技术领域Technical Field
本发明涉及半导体器件生产用耐热性压敏粘合片，其在不使用金属引线框的无基板半导体封装体的生产方法中用作临时固定芯片；以及使用该压敏粘合片生产半导体器件的方法。The present invention relates to a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, which is used as a temporary chip fixing method in a method for producing a substrate-less semiconductor package without using a metal lead frame; and a method for producing a semiconductor device using the pressure-sensitive adhesive sheet.
背景技术Background Art
近年来，在LSI的安装技术中CSP(芯片尺寸封装，Chip Size/Scale Package)技术备受关注。该技术中，就尺寸减少和高集成而言，由WLP(晶片级封装,Wafer LevelPackage)表示的以不使用基板而仅使用芯片的形式的封装为特别受关注的封装形式之一。根据WLP的生产方法，将不使用基板的以有序方式排列的多个半导体Si晶片芯片整体用包封树脂包封，然后通过切断分成单独的结构体，从而可有效生产与使用基板的常规封装体相比更小尺寸的封装体。In recent years, CSP (Chip Size/Scale Package) technology has attracted much attention in the installation technology of LSI. Among these technologies, in terms of size reduction and high integration, WLP (Wafer Level Package) is one of the packaging forms that has received particular attention, which is a form of packaging that uses only chips without using a substrate. According to the production method of WLP, a plurality of semiconductor Si wafer chips arranged in an orderly manner without using a substrate are encapsulated as a whole with an encapsulation resin, and then separated into separate structures by cutting, so that a smaller package can be effectively produced than a conventional package using a substrate.
此类WLP的生产方法需要将常规地固定在基板上的芯片固定在分开的支承体上。此外，在通过树脂包封成型为单独的封装体后必须解除固定。因而该支承体不应永久粘合而是必须可再剥离的。从该观点来看，存在使用压敏粘合带作为临时固定芯片用支承体的技术。The production method of this type of WLP requires that the chip, which is conventionally fixed on the substrate, be fixed on a separate support. In addition, the fixation must be released after being molded into a separate package by resin encapsulation. Therefore, the support should not be permanently bonded but must be removable. From this point of view, there is a technology that uses a pressure-sensitive adhesive tape as a support for temporarily fixing the chip.
发明内容Summary of the invention
发明要解决的问题Problem that the invention aims to solve
在使用压敏粘合带作为临时固定用支承体的无基板半导体封装体的生产方法中，由于当用树脂包封时的压力，芯片不被压敏粘合带支持，从指定位置偏移。另外，由于当粘合芯片时或当用树脂包封时的压力，芯片嵌入压敏粘合带，发生其中芯片面相对于包封树脂面变得突出的位置差异(偏移)。此外，由于包封树脂的固化和加热，压敏粘合带可变得强烈粘合至芯片表面，在剥离压敏粘合带时封装体会破损，产生残胶污染。In the production method of a substrate-free semiconductor package using a pressure-sensitive adhesive tape as a temporary fixing support, the chip is not supported by the pressure-sensitive adhesive tape due to the pressure when encapsulating with a resin, and is offset from a specified position. In addition, due to the pressure when bonding the chip or when encapsulating with a resin, the chip is embedded in the pressure-sensitive adhesive tape, and a position difference (offset) occurs in which the chip surface becomes prominent relative to the encapsulating resin surface. In addition, due to the curing and heating of the encapsulating resin, the pressure-sensitive adhesive tape may become strongly bonded to the chip surface, and the package body may be damaged when the pressure-sensitive adhesive tape is peeled off, resulting in residual adhesive contamination.
用于解决问题的方案Solutions for solving problems
本发明人等为了解决上述问题而进行了深入研究，结果发现，通过使用具有特定粘合力比的粘合剂层能够解决上述问题，从而完成了本发明。The present inventors have conducted intensive studies to solve the above problems and, as a result, have found that the above problems can be solved by using a pressure-sensitive adhesive layer having a specific adhesive force ratio, thereby completing the present invention.
即，本发明如下。That is, the present invention is as follows.
[1]一种半导体器件生产用耐热性压敏粘合片，其包括：基材层；和设置在所述基材层的一侧上的第一粘合剂层，[1] A heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, comprising: a base material layer; and a first adhesive layer provided on one side of the base material layer,
所述第一粘合剂层在100～150℃、优选130℃下加热3～10分钟后相对于不锈钢板的180°剥离粘合力N2与所述第一粘合剂层在20～25℃、优选23℃下相对于不锈钢板的180°剥离粘合力N1之比，即N2/N1≤2，优选N2/N1≤1.5。The ratio of the 180° peel adhesion N2 of the first adhesive layer relative to the stainless steel plate after heating at 100-150°C, preferably 130°C for 3-10 minutes to the 180° peel adhesion N1 of the first adhesive layer relative to the stainless steel plate at 20-25°C, preferably 23°C, that is, N2/N1≤2, preferably N2/N1≤1.5.
[2]根据[1]所述的半导体器件生产用耐热性压敏粘合片，所述第一粘合剂层在20～25℃、优选23℃下相对于不锈钢板的180°剥离粘合力N1为0.1～3.0N/20mm，优选为0.4～2.0N/20mm；[2] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [1], wherein the first adhesive layer has a 180° peeling adhesion N1 relative to a stainless steel plate at 20 to 25°C, preferably 23°C, of 0.1 to 3.0 N/20 mm, preferably 0.4 to 2.0 N/20 mm;
所述第一粘合剂层在100～150℃、优选130℃下加热3～10分钟后相对于不锈钢板的180°剥离粘合力N2为0.2～6.0N/20mm，优选为0.5～3.0N/20mm。The first adhesive layer has a 180° peeling adhesive strength N2 of 0.2 to 6.0 N/20 mm, preferably 0.5 to 3.0 N/20 mm, to a stainless steel plate after being heated at 100 to 150° C., preferably 130° C. for 3 to 10 minutes.
[3]根据[1]或[2]所述的半导体器件生产用耐热性压敏粘合片，所述第一粘合剂层包括丙烯酸系粘合剂；[3] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [1] or [2], wherein the first adhesive layer includes an acrylic adhesive;
所述第一粘合剂层的凝胶率大于70％；和/或The gel fraction of the first adhesive layer is greater than 70%; and/or
所述第一粘合剂层在20～25℃、优选23℃下的储能模量G'为0.5×105～12×105Pa；和/或The storage modulus G' of the first adhesive layer at 20-25°C, preferably 23°C, is 0.5×105 -12×105 Pa; and/or
所述丙烯酸系粘合剂的可溶性部分的重均分子量为80,000以下。The weight average molecular weight of the soluble part of the acrylic adhesive is 80,000 or less.
[4]根据[1]或[2]所述的半导体器件生产用耐热性压敏粘合片，所述半导体器件生产用耐热性压敏粘合片还包括第二粘合剂层，所述第二粘合剂层设置在所述基材层的与所述第一粘合剂层相反的一侧；[4] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [1] or [2], further comprising a second adhesive layer provided on the side of the substrate layer opposite to the first adhesive layer;
优选地，所述第二粘合剂层在20～25℃、优选23℃下相对于不锈钢板的15°剥离粘合力为2～100N/20mm，优选为2～50N/20mm；Preferably, the second adhesive layer has a 15° peel adhesion relative to a stainless steel plate at 20 to 25°C, preferably 23°C, of 2 to 100 N/20 mm, preferably 2 to 50 N/20 mm;
所述第二粘合剂层在150℃下加热4小时后相对于不锈钢板的15°剥离粘合力为3～130N/20mm，优选为3～100N/20mm。The second adhesive layer has a 15° peeling adhesive strength of 3 to 130 N/20 mm, preferably 3 to 100 N/20 mm, relative to a stainless steel plate after being heated at 150° C. for 4 hours.
[5]根据[4]所述的半导体器件生产用耐热性压敏粘合片，所述第二粘合剂层在20～25℃、优选23℃下的储能模量G'为0.8×105～2.5×105Pa；[5] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [4], wherein the second adhesive layer has a storage modulus G' of 0.8×105 to 2.5×105 Pa at 20 to 25° C., preferably 23° C.;
所述第二粘合剂层在150℃下的储能模量G'为0.5×105～1.6×105Pa。The storage modulus G' of the second adhesive layer at 150° C. is 0.5×105 -1.6×105 Pa.
[6]根据[4]所述的半导体器件生产用耐热性压敏粘合片，所述第二粘合剂层的凝胶率为40～90％；[6] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [4], wherein the gel fraction of the second adhesive layer is 40 to 90%;
优选地，所述第二粘合剂层的粘合剂的可溶性部分的重均分子量为2,000～6,000。Preferably, the weight average molecular weight of the soluble part of the adhesive of the second adhesive layer is 2,000 to 6,000.
[7]根据[1]或[2]所述的半导体器件生产用耐热性压敏粘合片，所述基材层选自由聚酯膜、聚酰胺膜、聚酰亚胺膜、聚苯硫醚膜、聚醚酰亚胺膜、聚酰胺酰亚胺膜、聚砜膜、聚醚酮膜、聚四氟乙烯膜、乙烯-四氟乙烯共聚物膜、全氟乙烯-丙烯共聚物膜、聚偏二氟乙烯膜、聚三氟氯乙烯膜以及乙烯和三氟氯乙烯以摩尔比1:1的交替共聚物膜组成的组中的至少一种。[7] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [1] or [2], wherein the substrate layer is at least one selected from the group consisting of polyester films, polyamide films, polyimide films, polyphenylene sulfide films, polyetherimide films, polyamideimide films, polysulfone films, polyetherketone films, polytetrafluoroethylene films, ethylene-tetrafluoroethylene copolymer films, perfluoroethylene-propylene copolymer films, polyvinylidene fluoride films, polychlorotrifluoroethylene films, and alternating copolymer films of ethylene and chlorotrifluoroethylene in a molar ratio of 1:1.
[8]根据[4]所述的半导体器件生产用耐热性压敏粘合片，所述半导体器件生产用耐热性压敏粘合片还包括第一离型膜和第二离型膜，所述第一离型膜设置在所述第一粘合剂层的与所述基材层相反的一侧，所述第二离型膜设置在所述第二粘合剂层的与所述基材层相反的一侧。[8] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [4], further comprising a first release film and a second release film, wherein the first release film is arranged on the side of the first adhesive layer opposite to the substrate layer, and the second release film is arranged on the side of the second adhesive layer opposite to the substrate layer.
[9]根据[4]所述的半导体器件生产用耐热性压敏粘合片，所述第一粘合剂层的厚度为5～50μm；所述第二粘合剂层的厚度为5～50μm。[9] The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to [4], wherein the thickness of the first adhesive layer is 5 to 50 μm; and the thickness of the second adhesive layer is 5 to 50 μm.
[10]一种用于生产半导体器件的方法，所述方法包括使用根据[1]～[9]中任一项所述的半导体器件生产用耐热性压敏粘合片。[10] A method for producing a semiconductor device, the method comprising using the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production according to any one of [1] to [9].
发明的效果Effects of the Invention
本发明提供一种半导体器件生产用耐热性压敏粘合片，其在不使用金属框的无基板半导体封装体的生产方法(例如，WLP的生产方法)中用作临时固定芯片的压敏粘合片。本发明的压敏粘合片能够支持芯片以便芯片在树脂包封步骤期间不转移，从而减少芯片从指定位置的偏移，并且通过在压敏粘合剂层中嵌入芯片的偏离小，本发明的压敏粘合片可在使用后轻轻剥离。另外，本发明的半导体器件生产用耐热性压敏粘合片能够在使用之后轻轻剥离而包封后对于包封树脂及芯片不发生残胶污染。The present invention provides a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, which is used as a pressure-sensitive adhesive sheet for temporarily fixing a chip in a production method of a substrate-free semiconductor package without a metal frame (e.g., a WLP production method). The pressure-sensitive adhesive sheet of the present invention can support the chip so that the chip does not shift during the resin encapsulation step, thereby reducing the deviation of the chip from the specified position, and the pressure-sensitive adhesive sheet of the present invention can be gently peeled off after use by embedding the chip in the pressure-sensitive adhesive layer. In addition, the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention can be gently peeled off after use without residual adhesive contamination of the encapsulation resin and the chip after encapsulation.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为示出使用本发明的半导体器件生产用耐热性压敏粘合片生产无基板BGA的步骤的流程图。FIG. 1 is a flow chart showing steps for producing a substrate-less BGA using the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention.
图2A至2F为示出无基板封装体的生产方法的示意图。2A to 2F are schematic diagrams illustrating a method of producing a substrate-less package.
图3A和3B为芯片不涉及偏离的情况和芯片涉及偏离的情况的对比图。3A and 3B are comparison diagrams of a case where the chip is not involved in deviation and a case where the chip is involved in deviation.
图4为示出半导体器件生产用耐热性压敏粘合片的图，其具有装配于其上的当用包封树脂包封时由于加热而变形的芯片。4 is a diagram showing a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production having a chip mounted thereon deformed by heat when encapsulated with an encapsulating resin.
图5为示出在剥离半导体器件生产用耐热性压敏粘合片时发生带电和残胶的图。FIG. 5 is a diagram showing the occurrence of charging and adhesive residue when peeling a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production.
图6为本发明的半导体器件生产用耐热性压敏粘合片的截面图。FIG. 6 is a cross-sectional view of the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention.
图7为本发明的半导体器件生产用耐热性压敏粘合片的另一实例的截面图。7 is a cross-sectional view of another example of the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention.
附图标记说明Description of Reference Numerals
1：芯片1: Chip
2：半导体器件生产用耐热性压敏粘合片2: Heat-resistant pressure-sensitive adhesive sheets for semiconductor device production
3：基板3: Substrate
4：包封树脂4: Encapsulation resin
5：电极5: Electrode
6：切割刀6: Cutting knife
7：切割环7: Cutting ring
8：切割带8: Cutting tape
9：残胶9: Residual glue
10：第一离型膜10: First release film
11：基材层11: Base material layer
12：第一粘合剂层12: First adhesive layer
13：第二粘合剂层13: Second adhesive layer
14：第二离型膜14: Second release film
具体实施方式DETAILED DESCRIPTION
作为克服上述问题的各种研究的结果，本发明人已发现如下。当将第一粘合剂层在100～150℃、优选130℃下加热3～10分钟后相对于不锈钢板的180°剥离粘合力N2与第一粘合剂层在20～25℃、优选23℃下相对于不锈钢板的180°剥离粘合力N1之比、即N2/N1≤2的粘合剂层用作在半导体器件生产用耐热性压敏粘合片中所使用的粘合剂层时，当用树脂包封芯片时，粘合的芯片不从指定位置偏移，可防止位置精度的劣化。并且，包封后，压敏粘合片可以在封装体不破损的情况下被剥离，对于包封树脂不发生残胶。As a result of various studies to overcome the above problems, the present inventors have found the following. When the ratio of the 180° peeling adhesion N2 of the first adhesive layer relative to the stainless steel plate after heating at 100 to 150°C, preferably 130°C for 3 to 10 minutes to the 180° peeling adhesion N1 of the first adhesive layer relative to the stainless steel plate at 20 to 25°C, preferably 23°C, i.e., N2/N1≤2, is used as an adhesive layer used in a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, when the chip is encapsulated with resin, the bonded chip does not shift from the specified position, and the degradation of the position accuracy can be prevented. Moreover, after encapsulation, the pressure-sensitive adhesive sheet can be peeled off without damaging the package body, and no residual adhesive will occur for the encapsulation resin.
[半导体器件生产用耐热性压敏粘合片][Heat-resistant pressure-sensitive adhesive sheet for semiconductor device production]
以下参考图6具体描述本发明的半导体器件生产用耐热性压敏粘合片2的实施方案。如图6所示，本发明的半导体器件生产用耐热性压敏粘合片2包括基材层11和第一粘合剂层12。An embodiment of the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention is specifically described below with reference to FIG6. As shown in FIG6, the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention includes a base material layer 11 and a first adhesive layer 12.
在另一个实施方式中，如图7所示，半导体器件生产用耐热性压敏粘合片2还可进一步包括在要固定和包封芯片的面相对的一侧的用于将粘合片固定至金属基板的粘合剂层，如第二粘合剂层13。In another embodiment, as shown in FIG. 7 , the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production may further include an adhesive layer for fixing the adhesive sheet to the metal substrate, such as a second adhesive layer 13 , on the side opposite to the surface to be fixed and encapsulated with the chip.
另外，为了保护使用前的半导体器件生产用耐热性压敏粘合片2中的粘合剂层的表面，可以在各个粘合剂层的表面上设置离型膜。例如，在第一粘合剂层的与基材层相反的一侧上设置第一离型膜10，在第二粘合剂层的与基材层相反的一侧上设置第二离型膜14。In addition, in order to protect the surface of the adhesive layer in the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production before use, a release film may be provided on the surface of each adhesive layer. For example, a first release film 10 is provided on the side of the first adhesive layer opposite to the substrate layer, and a second release film 14 is provided on the side of the second adhesive layer opposite to the substrate layer.
<基材层><Base material layer>
基材层的种类不特别限定，但优选使用在当用树脂包封时的加热条件下具有耐热性的基材。树脂包封步骤通常需要约175℃的温度。从该点上，优选使用具有在此类温度条件下不发生显著收缩或基材层自身不塌陷的这样的耐热性的材料。出于该原因，该材料优选具有在50～250℃的温度下的线性热膨胀系数为0.8×l0-5～5.6×l0-5/K。The type of the substrate layer is not particularly limited, but it is preferred to use a substrate having heat resistance under heating conditions when encapsulating with a resin. The resin encapsulation step generally requires a temperature of about 175°C. From this point of view, it is preferred to use a material having such heat resistance that no significant shrinkage occurs or the substrate layer itself does not collapse under such temperature conditions. For this reason, the material preferably has a linear thermal expansion coefficient of 0.8×10-5 to 5.6×10-5 /K at a temperature of 50 to 250°C.
在使用具有玻璃化转变温度低于固化包封树脂的加热温度的基材的情况下，在高于玻璃化转变温度的温度区域中的线性膨胀系数大于在低于玻璃化转变温度的温度区域中的线性膨胀系数，导致粘合的芯片的指定位置的精度的劣化。In the case of using a substrate having a glass transition temperature lower than the heating temperature for curing the encapsulating resin, the linear expansion coefficient in a temperature region higher than the glass transition temperature is larger than the linear expansion coefficient in a temperature region lower than the glass transition temperature, resulting in deterioration in the accuracy of the specified position of the bonded chip.
此外，在单轴或双轴拉伸的基材中，在高于玻璃化转变温度的温度下，由拉伸引起的伸长开始收缩，这导致粘合的芯片的指定位置的精度的劣化。为此，在树脂包封不使用金属引线框的无基板半导体芯片时，当用于通过被粘合至芯片来使用的半导体器件生产用耐热性压敏粘合片中的基材层的玻璃化转变温度超过180℃时，能够改进芯片的位置精度。In addition, in a uniaxially or biaxially stretched substrate, at a temperature higher than the glass transition temperature, the elongation caused by stretching begins to shrink, which leads to deterioration in the accuracy of the specified position of the bonded chip. For this reason, when a substrate-less semiconductor chip that does not use a metal lead frame is resin-encapsulated, when the glass transition temperature of the substrate layer in a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production used by being bonded to the chip exceeds 180°C, the position accuracy of the chip can be improved.
基材的实例优选选自由聚酯膜、聚酰胺膜、聚酰亚胺膜、聚苯硫醚膜、聚醚酰亚胺膜、聚酰胺酰亚胺膜、聚砜膜、聚醚酮膜、聚四氟乙烯膜、乙烯-四氟乙烯共聚物膜、全氟乙烯-丙烯共聚物膜、聚偏二氟乙烯膜、聚三氟氯乙烯膜、乙烯和三氟氯乙烯以摩尔比1:1的交替共聚物膜、纸基材(如玻璃纸、高质量纸和日本纸)、无纺布基材(如纤维素)和金属膜基材(如铝箔、SUS箔和Ni箔)组成的组中的至少一种。Examples of the substrate are preferably at least one selected from the group consisting of polyester films, polyamide films, polyimide films, polyphenylene sulfide films, polyetherimide films, polyamideimide films, polysulfone films, polyetherketone films, polytetrafluoroethylene films, ethylene-tetrafluoroethylene copolymer films, perfluoroethylene-propylene copolymer films, polyvinylidene fluoride films, polychlorotrifluoroethylene films, alternating copolymer films of ethylene and chlorotrifluoroethylene in a molar ratio of 1:1, paper substrates (such as glassine paper, high-quality paper and Japanese paper), nonwoven fabric substrates (such as cellulose) and metal film substrates (such as aluminum foil, SUS foil and Ni foil).
本发明中所使用的“玻璃化转变温度”是指在DMA法(拉伸法)中，在升温速度：5℃/min、样品宽度：5mm、卡盘间距：20mm和频率：10Hz的条件下证实的显示损耗角正切(tanδ)的峰的温度。The "glass transition temperature" used in the present invention refers to the temperature showing the peak of the loss tangent (tanδ) confirmed under the conditions of a heating rate of 5°C/min, a sample width of 5 mm, a chuck distance of 20 mm and a frequency of 10 Hz in a DMA method (tensile method).
基材具有5～200μm、优选10～150μm、并更优选20～100μm的厚度。厚度小于5μm的情况下，在固化包封树脂后剥离半导体器件生产用耐热性压敏粘合片时，半导体器件生产用耐热性压敏粘合片容易损坏，并可能不会被剥离，降低处理性。超过200μm的厚度增加成本，这是不优选的。The substrate has a thickness of 5 to 200 μm, preferably 10 to 150 μm, and more preferably 20 to 100 μm. In the case where the thickness is less than 5 μm, when the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production is peeled off after curing the encapsulating resin, the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production is easily damaged and may not be peeled off, reducing handling properties. A thickness exceeding 200 μm increases costs, which is not preferred.
另外，对于基材层，根据需要，也可以进行利用有机硅系、氟系、长链烷基系等的脱模剂的脱模和防污处理、酸处理、碱处理、底漆处理、电晕处理、等离子体处理等易粘接处理。The substrate layer may also be subjected to adhesion-facilitating treatments such as mold release using silicone-based, fluorine-based, long-chain alkyl-based release agents, antifouling treatment, acid treatment, alkali treatment, primer treatment, corona treatment, and plasma treatment, as needed.
<第一粘合剂层><First Adhesive Layer>
在用于本发明的第一粘合剂层中，粘合剂没有特别限定，只要其具有耐热性即可。从耐热性和成本的观点来看，优选第一粘合剂层包括丙烯酸系粘合剂。In the first adhesive layer used in the present invention, the adhesive is not particularly limited as long as it has heat resistance. From the viewpoint of heat resistance and cost, it is preferred that the first adhesive layer includes an acrylic adhesive.
丙烯酸系粘合剂是指将丙烯酸系聚合物作为基础聚合物(聚合物成分中的主要成分，即包含超过50重量％的成分)的粘合剂。对第一粘合剂层中的丙烯酸系聚合物的含量没有特别限制，从在第一粘合剂层中得到充分的粘接可靠性的观点来看，相对于第一粘合剂层总量(总重量，100质量％)，优选为60质量％以上，更优选为70质量％以上，进一步优选为80质量％以上。通过将丙烯酸系粘合剂中的丙烯酸系聚合物的含量调整为上述范围内，可以提供构成应力缓和性和耐久性更优异且对被粘物的粘附性优异的粘合剂层。Acrylic adhesive refers to an adhesive that uses acrylic polymer as a base polymer (the main component in the polymer component, i.e., a component containing more than 50% by weight). There is no particular restriction on the content of the acrylic polymer in the first adhesive layer. From the perspective of obtaining sufficient bonding reliability in the first adhesive layer, it is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more relative to the total amount of the first adhesive layer (total weight, 100% by weight). By adjusting the content of the acrylic polymer in the acrylic adhesive to within the above range, an adhesive layer having better stress relaxation and durability and excellent adhesion to an adherend can be provided.
此处公开的技术中的丙烯酸系聚合物优选为下述单体成分的聚合物：所述单体成分包含(甲基)丙烯酸烷基酯作为主要单体，可以根据需要进一步包含与上述主要单体具有共聚性的其他单体(共聚性单体)。此处主要单体是指构成丙烯酸系聚合物的单体成分中的主要成分，即该单体成分中包含超过50重量％的成分。在本说明书中，术语“(甲基)丙烯酸烷基酯”是指丙烯酸烷基酯和/或甲基丙烯酸烷基酯。The acrylic polymer in the technology disclosed herein is preferably a polymer of the following monomer components: the monomer component contains (meth) alkyl ester as a main monomer, and may further contain other monomers (copolymerizable monomers) copolymerizable with the above main monomer as required. The main monomer here refers to the main component in the monomer components constituting the acrylic polymer, that is, the component containing more than 50% by weight in the monomer components. In this specification, the term "alkyl (meth) acrylate" refers to alkyl acrylate and/or alkyl methacrylate.
上述的(甲基)丙烯酸烷基酯是用于构成丙烯酸系聚合物的主要单体成分，承担着表现出粘接性等作为粘合剂(或粘合剂层)的基本特性的作用。(甲基)丙烯酸烷基酯具有对作为基础聚合物的丙烯酸系聚合物赋予柔软性的倾向，因此，具有发挥出使第一粘合剂层表现出密合性及粘合性的效果的倾向。(甲基)丙烯酸烷基酯具有对作为基础聚合物的丙烯酸类聚合物赋予硬度的倾向，因此，具有发挥出使第一粘合剂层表现出再剥离性及力的传递性的效果的倾向。The above-mentioned alkyl (meth)acrylate is a main monomer component for constituting an acrylic polymer, and plays a role in expressing basic characteristics as an adhesive (or adhesive layer), such as adhesion. The alkyl (meth)acrylate tends to impart flexibility to the acrylic polymer as a base polymer, and therefore, tends to exert an effect of causing the first adhesive layer to exhibit adhesion and adhesiveness. The alkyl (meth)acrylate tends to impart hardness to the acrylic polymer as a base polymer, and therefore, tends to exert an effect of causing the first adhesive layer to exhibit removability and force transmission.
作为(甲基)丙烯酸烷基酯，优选为烷基的碳原子数为4～20的(甲基)丙烯酸烷基酯。作为烷基的碳原子数为4～20的(甲基)丙烯酸烷基酯的具体例，没有特别限制，可以列举：(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯和(甲基)丙烯酸二十烷基酯。这些之中，优选丙烯酸正丁酯(BA)和丙烯酸-2-乙基己酯(2EHA)。(甲基)丙烯酸烷基酯可以单独使用或者组合两种以上使用。As the alkyl (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 4 to 20 carbon atoms is preferred. Specific examples of the alkyl (meth)acrylate having an alkyl group with 4 to 20 carbon atoms are not particularly limited, and include n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Among these, n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) are preferred. The (meth)acrylic acid alkyl esters may be used alone or in combination of two or more.
(甲基)丙烯酸烷基酯占构成丙烯酸系聚合物的单体成分的比例优选为90～95重量份，基于丙烯酸系聚合物的全部单体成分100重量份。通过这样的组成的单体成分，从而能够得到构件的保持性能优异的粘合片。The ratio of the (meth)acrylic acid alkyl ester to the monomer components constituting the acrylic polymer is preferably 90 to 95 parts by weight based on 100 parts by weight of all the monomer components of the acrylic polymer. With such a composition of monomer components, a PSA sheet having excellent member holding performance can be obtained.
作为共聚性单体，可以适宜地使用具有极性基团的单体。具有极性基团的单体对于在丙烯酸系聚合物中导入交联点、或者提高丙烯酸系聚合物的内聚力是有用的。共聚性单体可以单独使用1种或将2种以上组合使用。As the copolymerizable monomer, a monomer having a polar group can be suitably used. The monomer having a polar group is useful for introducing a crosslinking point into the acrylic polymer or increasing the cohesive force of the acrylic polymer. The copolymerizable monomer can be used alone or in combination of two or more.
作为共聚性单体的非限定性的具体实例，例如可列举出含羟基单体(含有羟基的单体)、含羧基单体(含有羧基的单体)、含磺酸基单体、含有磷酸基的单体、含环氧基的单体、含氰基的单体、含异氰酸酯基的单体、含酰胺基的单体、具有含氮原子的环的单体、具有琥珀酰亚胺骨架的单体、马来酰亚胺类、衣康酰亚胺类、(甲基)丙烯酸氨基烷基酯类、(甲基)丙烯酸烷氧基烷基酯类、乙烯基酯类、乙烯基醚类、芳香族乙烯基化合物、烯烃类等。Specific non-limiting examples of copolymerizable monomers include hydroxyl group-containing monomers (hydroxyl group-containing monomers), carboxyl group-containing monomers (carboxyl group-containing monomers), sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, isocyanate group-containing monomers, amide group-containing monomers, monomers having a nitrogen atom-containing ring, monomers having a succinimide skeleton, maleimides, itaconimides, (meth)acrylic acid aminoalkyl esters, (meth)acrylic acid alkoxyalkyl esters, vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, and the like.
含羟基单体是指分子内具有至少一个羟基的单体。在用于构成丙烯酸系聚合物的单体成分包含含羟基单体的情况下，即，丙烯酸系聚合物包含源自含羟基单体的单体单元的情况下，在第一粘合剂层中容易得到粘接性、适度的内聚力。另外，在丙烯酸系聚合物包含源自含羟基单体的单体单元且第一粘合剂层包含异氰酸酯系交联剂等交联剂(固化剂)的情况下，含羟基单体单元可在其与该交联剂之间进行交联，因此在第一粘合剂层中容易得到硬度、良好的粘接可靠性。本实施方式的丙烯酸系聚合物可以使用1种含羟基单体，也可以使用2种以上的含羟基单体。A hydroxyl-containing monomer refers to a monomer having at least one hydroxyl group in the molecule. When the monomer component used to constitute the acrylic polymer includes a hydroxyl-containing monomer, that is, when the acrylic polymer includes a monomer unit derived from a hydroxyl-containing monomer, it is easy to obtain adhesion and moderate cohesion in the first adhesive layer. In addition, when the acrylic polymer includes a monomer unit derived from a hydroxyl-containing monomer and the first adhesive layer includes a cross-linking agent (curing agent) such as an isocyanate cross-linking agent, the hydroxyl-containing monomer unit can be cross-linked between it and the cross-linking agent, so it is easy to obtain hardness and good bonding reliability in the first adhesive layer. The acrylic polymer of this embodiment can use one hydroxyl-containing monomer, or two or more hydroxyl-containing monomers.
在一个优选实施方式中，含羟基单体优选包含具有伯羟基的含羟基单体和/或具有仲羟基的含羟基单体。In a preferred embodiment, the hydroxyl group-containing monomer preferably comprises a hydroxyl group-containing monomer having a primary hydroxyl group and/or a hydroxyl group-containing monomer having a secondary hydroxyl group.
在一个优选实施方式中，含羟基单体包含含羟基的(甲基)丙烯酸酯和/或不饱和醇。In a preferred embodiment, the hydroxyl group-containing monomer comprises a hydroxyl group-containing (meth)acrylate and/or an unsaturated alcohol.
作为含羟基的(甲基)丙烯酸酯的实例，例如可列举出：(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-3-羟基丙酯、(甲基)丙烯酸-2-羟基丁酯、(甲基)丙烯酸-3-羟基丁酯、(甲基)丙烯酸-4-羟基丁酯、(甲基)丙烯酸-6-羟基己酯、(甲基)丙烯酸羟基辛酯、(甲基)丙烯酸羟基癸酯、(甲基)丙烯酸羟基月桂酯、(甲基)丙烯酸(4-羟甲基环己基)甲酯、丙烯酸聚己内酯等。Examples of the hydroxyl-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and polycaprolactone acrylate.
作为不饱和醇的实例，例如可列举出：乙烯醇、烯丙醇等。Examples of the unsaturated alcohol include vinyl alcohol and allyl alcohol.
对含羟基单体的含量没有特别限定，从在第一粘合剂层中得到充分的粘接性、适度的内聚力的观点；或在第一粘合剂层包含异氰酸酯系交联剂等交联剂的情况下，在该粘合剂层中得到硬度、良好的粘接可靠性的观点来看，基于丙烯酸系聚合物的全部单体成分100重量份，含羟基单体的含量为0.1～5重量份，优选2～4重量份。含羟基单体的含量小于0.1重量份时，得不到充分的粘接性。含羟基单体的含量大于5重量份时，第一粘合剂层变得过硬，粘接可靠性降低。There is no particular limitation on the content of the hydroxyl-containing monomer. From the perspective of obtaining sufficient adhesion and appropriate cohesion in the first adhesive layer; or from the perspective of obtaining hardness and good bonding reliability in the adhesive layer when the first adhesive layer contains a crosslinking agent such as an isocyanate crosslinking agent, the content of the hydroxyl-containing monomer is 0.1 to 5 parts by weight, preferably 2 to 4 parts by weight, based on 100 parts by weight of all monomer components of the acrylic polymer. When the content of the hydroxyl-containing monomer is less than 0.1 parts by weight, sufficient adhesion cannot be obtained. When the content of the hydroxyl-containing monomer is greater than 5 parts by weight, the first adhesive layer becomes too hard and the bonding reliability is reduced.
含羧基单体是指分子内具有至少一个羧基的单体。通过使单体成分包含含羧基单体，容易得到具有良好耐久性的粘合片。另外，粘合剂层与被粘物的密合性也可以进一步提高。Carboxyl group-containing monomer refers to a monomer having at least one carboxyl group in the molecule. By making the monomer component include carboxyl group-containing monomer, it is easy to obtain an adhesive sheet with good durability. In addition, the adhesion of the adhesive layer to the adherend can also be further improved.
作为含羧基单体，优选包含烯属不饱和单羧酸和/或烯属不饱和二羧酸及其酸酐。作为烯属不饱和单羧酸的实例，例如可列举出：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、巴豆酸和异巴豆酸等。作为烯属不饱和二羧酸及其酸酐的实例，例如可列举出：富马酸、衣康酸、马来酸、柠康酸、马来酸酐和衣康酸酐等。这些之中，优选丙烯酸、甲基丙烯酸和马来酸。上述含羧基单体可以单独使用任意1种或组合使用2种以上。As the carboxyl-containing monomer, it is preferred to include ethylenically unsaturated monocarboxylic acids and/or ethylenically unsaturated dicarboxylic acids and their anhydrides. Examples of ethylenically unsaturated monocarboxylic acids include, for example, acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, crotonic acid, and isocrotonic acid. Examples of ethylenically unsaturated dicarboxylic acids and their anhydrides include, for example, fumaric acid, itaconic acid, maleic acid, citraconic acid, maleic anhydride, and itaconic anhydride. Among these, acrylic acid, methacrylic acid, and maleic acid are preferred. The above-mentioned carboxyl-containing monomers may be used alone in any one kind or in combination of two or more kinds.
对含羧基单体的含量没有特别限定，例如相对于丙烯酸系聚合物的全部单体成分100重量份，含羧基单体的含量优选为1～5重量份，更优选为2～4重量份。通过将含羧基单体的含量设在上述范围内，可以提高粘接强度，进一步实现保持粘接性能优异的粘合片。含羧基单体的含量小于1重量份时，得不到充分的粘接性。含羧基单体的含量大于5重量份时，粘接可靠性降低。The content of the carboxyl group-containing monomer is not particularly limited. For example, relative to 100 parts by weight of all monomer components of the acrylic polymer, the content of the carboxyl group-containing monomer is preferably 1 to 5 parts by weight, and more preferably 2 to 4 parts by weight. By setting the content of the carboxyl group-containing monomer within the above range, the bonding strength can be increased, and a pressure-sensitive adhesive sheet having excellent bonding performance can be further achieved. When the content of the carboxyl group-containing monomer is less than 1 part by weight, sufficient adhesion cannot be obtained. When the content of the carboxyl group-containing monomer is greater than 5 parts by weight, the bonding reliability is reduced.
作为含磺酸基单体，例如可列举出：苯乙烯磺酸、烯丙基磺酸、乙烯基磺酸钠、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺基丙酯、(甲基)丙烯酰氧基萘磺酸等。Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic acid.
作为含有磷酸基的单体，例如可列举出：2-羟基乙基丙烯酰基磷酸酯等。As a monomer containing a phosphoric acid group, 2-hydroxyethyl acryloyl phosphate etc. are mentioned, for example.
作为含环氧基的单体，例如可列举出：(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸-2-乙基缩水甘油醚等含环氧基的丙烯酸酯、烯丙基缩水甘油醚、(甲基)丙烯酸缩水甘油醚等。Examples of the epoxy group-containing monomer include epoxy group-containing acrylates such as glycidyl (meth)acrylate and 2-ethyl glycidyl (meth)acrylate, allyl glycidyl ether, and glycidyl (meth)acrylate.
作为含氰基的单体，例如可列举出：丙烯腈、甲基丙烯腈等。Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
作为含异氰酸酯基的单体，例如可列举出：(甲基)丙烯酸2-异氰酸根合乙酯等。As an isocyanate group-containing monomer, 2-isocyanatoethyl (meth)acrylate etc. are mentioned, for example.
作为含酰胺基的单体，例如可列举出：(甲基)丙烯酰胺；N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、N,N-二丙基(甲基)丙烯酰胺、N,N-二异丙基(甲基)丙烯酰胺、N,N-二(正丁基)(甲基)丙烯酰胺、N,N-二(叔丁基)(甲基)丙烯酰胺等N,N-二烷基(甲基)丙烯酰胺；N-乙基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N-丁基(甲基)丙烯酰胺、N-正丁基(甲基)丙烯酰胺等N-烷基(甲基)丙烯酰胺；N-乙烯基乙酰胺等N-乙烯基羧酸酰胺类；N,N-二甲基氨基丙基(甲基)丙烯酰胺、羟基乙基丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-羟乙基(甲基)丙烯酰胺、N-羟甲基丙烷(甲基)丙烯酰胺、N-甲氧基甲基(甲基)丙烯酰胺、N-甲氧基乙基(甲基)丙烯酰胺、N-丁氧基甲基(甲基)丙烯酰胺、N-(甲基)丙烯酰基吗啉等。Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di(n-butyl) (meth)acrylamide, N,N-di(tert-butyl) (meth)acrylamide and the like N,N-dialkyl (meth)acrylamide; N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide and the like; N-alkyl (meth)acrylamide, such as amine, N-n-butyl (meth)acrylamide, etc.; N-vinyl carboxylic acid amides such as N-vinylacetamide; N,N-dimethylaminopropyl (meth)acrylamide, hydroxyethyl acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methylolpropane (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-(meth)acryloyl morpholine, etc.
作为具有含氮原子的环的单体，例如可列举出：N-乙烯基-2-吡咯烷酮、N-甲基乙烯基吡咯烷酮、N-乙烯基吡啶、N-乙烯基哌啶酮、N-乙烯基嘧啶、N-乙烯基哌嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基噁唑、N-(甲基)丙烯酰基-2-吡咯烷酮、N-(甲基)丙烯酰基哌啶、N-(甲基)丙烯酰基吡咯烷、N-乙烯基吗啉、N-乙烯基-3-吗啉酮、N-乙烯基-2-己内酰胺、N-乙烯基-1,3-噁嗪-2-酮、N-乙烯基-3,5-吗啉二酮、N-乙烯基吡唑、N-乙烯基异噁唑、N-乙烯基噻唑、N-乙烯基异噻唑、N-乙烯基哒嗪等(例如N-乙烯基-2-己内酰胺等内酰胺类)。Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazine-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, and N-vinylpyridazine (for example, lactams such as N-vinyl-2-caprolactam).
作为具有琥珀酰亚胺骨架的单体，例如可列举出：N-(甲基)丙烯酰氧基亚甲基琥珀酰亚胺、N-(甲基)丙烯酰基-6-氧六亚甲基琥珀酰亚胺、N-(甲基)丙烯酰基-8-氧六亚甲基琥珀酰亚胺等。Examples of the monomer having a succinimide skeleton include N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, and N-(meth)acryloyl-8-oxyhexamethylenesuccinimide.
作为马来酰亚胺类，例如可列举出：N-环己基马来酰亚胺、N-异丙基马来酰亚胺、N-月桂基马来酰亚胺、N-苯基马来酰亚胺等。Examples of maleimides include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide.
作为衣康酰亚胺类，例如可列举出：N-甲基衣康酰亚胺、N-乙基衣康酰亚胺、N-丁基衣康酰亚胺、N-辛基衣康酰亚胺、N-2-乙基己基衣康酰亚胺、N-环己基衣康酰亚胺、N-月桂基衣康酰亚胺等。Examples of itaconimides include N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, and N-lauryl itaconimide.
作为(甲基)丙烯酸氨基烷基酯类，例如可列举出：(甲基)丙烯酸氨基乙酯、(甲基)丙烯酸N,N-二甲基氨基乙酯、(甲基)丙烯酸N,N-二乙基氨基乙酯、(甲基)丙烯酸叔丁基氨基乙酯。Examples of the aminoalkyl (meth)acrylates include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate.
作为(甲基)丙烯酸烷氧基烷基酯类，例如可列举出：(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丙氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基丙酯等。Examples of the alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and ethoxypropyl (meth)acrylate.
作为乙烯基酯类，例如可列举出：乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯等。Examples of the vinyl esters include vinyl acetate, vinyl propionate, and vinyl laurate.
作为乙烯基醚类，例如可列举出：甲基乙烯基醚、乙基乙烯基醚等乙烯基烷基醚。Examples of the vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
作为芳香族乙烯基化合物，例如可列举出：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、氯苯乙烯、氯甲基苯乙烯等。Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and chloromethylstyrene.
作为烯烃类，例如可列举出：乙烯、丁二烯、异戊二烯、异丁烯等。Examples of the olefins include ethylene, butadiene, isoprene, and isobutylene.
得到丙烯酸系聚合物的方法没有特别限定，可以适宜采用溶液聚合法、乳液聚合法、本体聚合法、悬浮聚合法、光聚合法等作为丙烯酸系聚合物的合成方法已知的各种聚合方法。例如，可以优选采用溶液聚合法。作为进行溶液聚合时的单体供给方法，可以适当采用一次性供给全部单体原料的分批投料方式、连续供给(滴加)方式、分着供给(滴加)方式等。进行溶液聚合时的聚合温度可以根据使用的单体及溶剂的种类、聚合引发剂的种类等而适当选择，例如可以设定为20～170℃左右(典型的是40～140℃左右)。The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as the synthesis methods of acrylic polymers, such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization, can be appropriately adopted. For example, solution polymerization can be preferably adopted. As a monomer supply method when performing solution polymerization, a batch feeding method of supplying all monomer raw materials at one time, a continuous supply (drip) method, a divided supply (drip) method, etc. can be appropriately adopted. The polymerization temperature when performing solution polymerization can be appropriately selected according to the types of monomers and solvents used, the type of polymerization initiator, etc., and can be set to, for example, about 20 to 170°C (typically about 40 to 140°C).
溶液聚合中使用的溶剂(聚合溶剂)可以从现有公知的有机溶剂中适当选择。例如，可以使用选自甲苯等芳香族化合物类(典型地为芳香烃类)；乙酸乙酯等乙酸酯类；己烷、环己烷等脂肪族或脂环式烃类；1,2-二氯乙烷等卤代烷烃类；异丙醇等低级醇类(例如碳原子数1～4的一元醇类)；叔丁基甲基醚等醚类；甲乙酮等酮类等中的任意一种溶剂或两种以上的混合溶剂。The solvent (polymerization solvent) used in the solution polymerization can be appropriately selected from the conventionally known organic solvents. For example, any one solvent or a mixed solvent of two or more selected from aromatic compounds such as toluene (typically aromatic hydrocarbons); acetates such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; halogenated alkanes such as 1,2-dichloroethane; lower alcohols such as isopropanol (e.g. monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone, etc. can be used.
聚合中使用的引发剂可以根据聚合方法的种类从现有公知的聚合引发剂中适当选择。例如，可以优选使用2,2’-偶氮二异丁腈(AIBN)等偶氮类聚合引发剂中的一种或两种以上。作为聚合引发剂的其它示例，可以列举：过硫酸钾等过硫酸盐；过氧化苯甲酰、过氧化氢等过氧化物类引发剂；苯基取代乙烷等取代乙烷类引发剂；芳香族羰基化合物等。作为聚合引发剂的另外的其它示例，可以列举由过氧化物与还原剂的组合得到的氧化还原类引发剂。这样的聚合引发剂可以单独使用一种或组合使用两种以上。聚合引发剂的使用量为通常的使用量即可，例如，相对于全部单体成分100重量份，可以从约0.005重量份～约1重量份(典型地为约0.01重量份～约1重量份)的范围选择。The initiator used in the polymerization can be appropriately selected from the existing known polymerization initiators according to the type of polymerization method. For example, one or more of the azo polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used. As other examples of polymerization initiators, there can be listed: persulfates such as potassium persulfate; peroxide initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane initiators such as phenyl substituted ethane; aromatic carbonyl compounds, etc. As other examples of polymerization initiators, redox initiators obtained by combining peroxides and reducing agents can be listed. Such polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used can be the usual amount, for example, it can be selected from the range of about 0.005 parts by weight to about 1 part by weight (typically about 0.01 parts by weight to about 1 part by weight) relative to 100 parts by weight of all monomer components.
通过上述溶液聚合，可以得到丙烯酸系聚合物溶解在有机溶剂中的形态的聚合反应液。在此公开的技术中的粘合剂层可以由包含上述聚合反应液或对该反应液实施适当的后处理而得到的丙烯酸系聚合物溶液的粘合剂组合物形成。作为上述丙烯酸系聚合物溶液来说，可以使用根据需要将上述聚合反应液调节为适当的粘度(浓度)后的丙烯酸系聚合物溶液。或者，也可以使用通过除溶液聚合以外的聚合方法(例如乳液聚合、光聚合、本体聚合等)合成丙烯酸系聚合物、并使该丙烯酸系聚合物溶解于有机溶剂而制备成的丙烯酸系聚合物溶液。Through the above-mentioned solution polymerization, a polymerization reaction liquid in the form of an acrylic polymer dissolved in an organic solvent can be obtained. The adhesive layer in the technology disclosed herein can be formed by an adhesive composition containing the above-mentioned polymerization reaction liquid or an acrylic polymer solution obtained by subjecting the reaction liquid to appropriate post-treatment. As the above-mentioned acrylic polymer solution, an acrylic polymer solution in which the above-mentioned polymerization reaction liquid is adjusted to an appropriate viscosity (concentration) as required can be used. Alternatively, an acrylic polymer solution prepared by synthesizing an acrylic polymer by a polymerization method other than solution polymerization (such as emulsion polymerization, photopolymerization, bulk polymerization, etc.) and dissolving the acrylic polymer in an organic solvent can also be used.
在此公开的技术中的丙烯酸系粘合剂的可溶性部分的重均分子量(Mw)没有特别限制，从粘合性能的观点考虑，丙烯酸系粘合剂的可溶性部分的Mw优选处于80,000以下的范围，更优选为5,000以上。重均分子量小于5,000时，具有粘合剂层的凝聚力降低的倾向，有时在被粘物的固定时发生偏移，或者剥离时产生残胶。另一方面，重均分子量超过80,000时，具有凝聚力因聚合物的缠结带来的效果而增大从而流动性降低的倾向，有时不能得到足够的粘合面积而无法进行被粘物的固定。在此，Mw是指通过GPC(凝胶渗透色谱法)得到的标准聚苯乙烯换算的值。GPC装置例如可以使用型号名“HLC-8320GPC”(柱：TSKgelGMH-H(S)、东曹公司制)。The weight average molecular weight (Mw) of the soluble part of the acrylic adhesive in the technology disclosed herein is not particularly limited. From the viewpoint of adhesive performance, the Mw of the soluble part of the acrylic adhesive is preferably in the range of 80,000 or less, and more preferably 5,000 or more. When the weight average molecular weight is less than 5,000, there is a tendency that the cohesive force of the adhesive layer is reduced, and sometimes an offset occurs when the adherend is fixed, or residual glue is produced when peeled off. On the other hand, when the weight average molecular weight exceeds 80,000, there is a tendency that the cohesive force increases due to the effect of the entanglement of the polymer, thereby reducing the fluidity, and sometimes sufficient bonding area cannot be obtained and the adherend cannot be fixed. Here, Mw refers to the value converted to standard polystyrene obtained by GPC (gel permeation chromatography). The GPC device can use, for example, the model name "HLC-8320GPC" (column: TSKgelGMH-H (S), manufactured by Tosoh Corporation).
在这里公开的第一粘合剂层中，为了调节内聚力等，还可以使用交联剂。交联剂可以使用通常使用的交联剂，例如可列举环氧系交联剂、异氰酸酯系交联剂、氮丙啶系交联剂、三聚氰胺系交联剂、金属螯合物系交联剂等。这些交联剂可以单独使用，也可以混合两种以上使用。In the first adhesive layer disclosed herein, a crosslinking agent may be used to adjust the cohesive force, etc. The crosslinking agent may be a commonly used crosslinking agent, for example, epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, metal chelate crosslinking agents, etc. These crosslinking agents may be used alone or in combination of two or more.
在一个优选实施方式中，交联剂优选包含环氧系交联剂和/或异氰酸酯系交联剂。通过使用这两种交联剂，能够充分提高粘合剂层的凝聚力。另外，在包含基材层的构成中，能够保证对该基材层的良好的粘附性。在此公开的技术中的粘合剂层可以以交联反应后的形态、交联反应前的形态、部分进行了交联反应的形态、这些形态的中间形态或复合形态等形态含有上述交联剂。上述交联剂典型地仅以交联反应后的形态包含于粘合剂层中。In a preferred embodiment, the crosslinking agent preferably comprises an epoxy crosslinking agent and/or an isocyanate crosslinking agent. By using these two crosslinking agents, the cohesive force of the adhesive layer can be fully improved. In addition, in the formation comprising a substrate layer, good adhesion to the substrate layer can be guaranteed. The adhesive layer in the technology disclosed herein can contain the above-mentioned crosslinking agent in the form after the crosslinking reaction, the form before the crosslinking reaction, the form partially subjected to the crosslinking reaction, the intermediate form of these forms or the composite form. The above-mentioned crosslinking agent is typically only included in the adhesive layer in the form after the crosslinking reaction.
作为环氧系交联剂，可以没有特别限制地使用一分子中具有两个以上环氧基的化合物。优选一分子中具有3～5个环氧基的环氧系交联剂。环氧系交联剂可以单独使用一种或组合使用两种以上。As the epoxy crosslinking agent, a compound having two or more epoxy groups in one molecule can be used without particular limitation. An epoxy crosslinking agent having 3 to 5 epoxy groups in one molecule is preferred. The epoxy crosslinking agent can be used alone or in combination of two or more.
作为环氧系交联剂的具体例，没有特别限制，可以列举例如：N,N,N’,N’-四缩水甘油基间苯二甲胺、1,3-双(N,N-二缩水甘油基氨基甲基)环己烷、1,6-己二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、聚甘油多缩水甘油醚等。作为环氧类交联剂的市售品，可以列举三菱瓦斯化学公司制造的商品名“TETRAD-C”和商品名“TETRAD-X”、DIC公司制造的商品名“EPICLON CR-5L”、长濑化成公司制造的商品名“DENACOL EX-512”、日产化学工业公司制造的商品名“TEPIC-G”等。Specific examples of epoxy crosslinking agents are not particularly limited, and examples thereof include N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, etc. Commercially available products of epoxy crosslinking agents include "TETRAD-C" and "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., "EPICLON CR-5L" manufactured by DIC Corporation, "DENACOL EX-512" manufactured by Nagase Chemicals Co., Ltd., and "TEPIC-G" manufactured by Nissan Chemical Industries, Ltd.
环氧系交联剂的使用量没有特别限制。环氧系交联剂的使用量例如相对于丙烯酸系聚合物100重量份优选设定为0.1～2重量份。The amount of the epoxy crosslinking agent used is not particularly limited and is preferably set to 0.1 to 2 parts by weight based on 100 parts by weight of the acrylic polymer.
在含有环氧系交联剂的实施方式中，环氧系交联剂的环氧当量优选为80～120g/eq。In the embodiment containing an epoxy-based crosslinking agent, the epoxy equivalent of the epoxy-based crosslinking agent is preferably 80 to 120 g/eq.
作为异氰酸酯系交联剂，可以优选使用多官能异氰酸酯(是指每一分子具有平均两个以上异氰酸酯基的化合物，包括具有异氰脲酸酯结构的化合物)。异氰酸酯系交联剂可以单独使用一种或组合使用两种以上。As the isocyanate crosslinking agent, polyfunctional isocyanate (a compound having an average of two or more isocyanate groups per molecule, including a compound having an isocyanurate structure) can be preferably used. The isocyanate crosslinking agent can be used alone or in combination of two or more.
作为多官能异氰酸酯的实例，可以列举脂肪族多异氰酸酯类、脂环族多异氰酸酯类、芳香族多异氰酸酯类等。Examples of the polyfunctional isocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and the like.
作为脂肪族多异氰酸酯类的具体例，可以列举：1,2-亚乙基二异氰酸酯；1,2-丁二异氰酸酯、1,3-丁二异氰酸酯、1,4-丁二异氰酸酯等丁二异氰酸酯；1,2-己二异氰酸酯、1,3-己二异氰酸酯、1,4-己二异氰酸酯、1,5-己二异氰酸酯、1,6-己二异氰酸酯、2,5-己二异氰酸酯等己二异氰酸酯；2-甲基-1,5-戊二异氰酸酯、3-甲基-1,5-戊二异氰酸酯、赖氨酸二异氰酸酯等。Specific examples of aliphatic polyisocyanates include: 1,2-ethylene diisocyanate; 1,2-butylene diisocyanate, 1,3-butylene diisocyanate, 1,4-butylene diisocyanate and other butylene diisocyanates; 1,2-hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate and other hexamethylene diisocyanates; 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, lysine diisocyanate and the like.
作为脂环族多异氰酸酯类的具体例，可以列举：异佛尔酮二异氰酸酯；1,2-环己基二异氰酸酯、1,3-环己基二异氰酸酯、1,4-环己基二异氰酸酯等环己基二异氰酸酯；1,2-环戊基二异氰酸酯、1,3-环戊基二异氰酸酯等环戊基二异氰酸酯；氢化苯二亚甲基二异氰酸酯、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、氢化四甲基二甲苯二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯等。Specific examples of alicyclic polyisocyanates include isophorone diisocyanate; cyclohexyl diisocyanates such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, and 1,4-cyclohexyl diisocyanate; cyclopentyl diisocyanates such as 1,2-cyclopentyl diisocyanate and 1,3-cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.
作为芳香族多异氰酸酯类的具体例，可以列举：2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、4,4’-二苯醚二异氰酸酯、2-硝基联苯-4,4’-二异氰酸酯、2,2’-二苯基丙烷-4,4’-二异氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二异氰酸酯、4,4’-二苯基丙烷二异氰酸酯、间苯二异氰酸酯、对苯二异氰酸酯、萘-1,4-二异氰酸酯、萘-1,5-二异氰酸酯、3,3’-二甲氧基联苯-4,4’-二异氰酸酯、苯二亚甲基-1,4-二异氰酸酯、苯二亚甲基-1,3-二异氰酸酯等。Specific examples of aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrobiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, Isocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, etc.
作为优选的多官能异氰酸酯，可以例示每一分子平均具有3个以上异氰酸酯基的多官能异氰酸酯。所述三官能以上的异氰酸酯可以是双官能或三官能以上的异氰酸酯的多聚物(典型地为二聚物或三聚物)、衍生物(例如多元醇与两分子以上的多官能异氰酸酯的加成反应产物)、聚合物等。可以列举例如：二苯基甲烷二异氰酸酯的二聚物或三聚物、己二异氰酸酯的异氰脲酸酯形式(异氰脲酸酯结构的三聚物加成物)、三羟甲基丙烷与甲苯二异氰酸酯的反应产物、三羟甲基丙烷与己二异氰酸酯的反应产物、多亚甲基多苯基异氰酸酯、聚醚多异氰酸酯、聚酯多异氰酸酯等多官能异氰酸酯。作为所述多官能异氰酸酯的市售品，可以列举旭化成化学公司制造的商品名“DURANATE TPA-100”、日本聚氨酯工业公司制造的商品名“CORONATE L”、日本聚氨酯工业公司制造的商品名“CORONATE HL”、日本聚氨酯工业公司制造的商品名“CORONATE HK”、日本聚氨酯工业公司制造的商品名“CORONATE HX”、日本聚氨酯工业公司制造的商品名“CORONATE2096”等。As preferred polyfunctional isocyanates, polyfunctional isocyanates having an average of 3 or more isocyanate groups per molecule can be exemplified. The trifunctional or higher isocyanates can be polymers (typically dimers or trimers), derivatives (e.g., addition reaction products of polyols and two or more molecules of polyfunctional isocyanates), polymers, etc. of difunctional or trifunctional isocyanates. For example, polyfunctional isocyanates such as dimers or trimers of diphenylmethane diisocyanate, isocyanurate forms of hexamethylene diisocyanate (trimer adducts of isocyanurate structures), reaction products of trimethylolpropane and toluene diisocyanate, reaction products of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanates, polyether polyisocyanates, and polyester polyisocyanates can be cited. Examples of commercially available products of the polyfunctional isocyanate include "DURANATE TPA-100" manufactured by Asahi Kasei Chemicals, "CORONATE L" manufactured by Nippon Polyurethane Industries, "CORONATE HL" manufactured by Nippon Polyurethane Industries, "CORONATE HK" manufactured by Nippon Polyurethane Industries, "CORONATE HX" manufactured by Nippon Polyurethane Industries, and "CORONATE 2096" manufactured by Nippon Polyurethane Industries.
在含有异氰酸酯系交联剂的实施方式中，异氰酸酯系交联剂中异氰酸酯基含量(NCO含量)优选为7～15％。In the embodiment containing an isocyanate-based crosslinking agent, the isocyanate group content (NCO content) in the isocyanate-based crosslinking agent is preferably 7 to 15%.
异氰酸酯系交联剂的使用量没有特别限制。异氰酸酯系交联剂的使用量例如相对于丙烯酸系聚合物100重量份可以设定为1～5重量份。The amount of the isocyanate crosslinking agent used is not particularly limited and can be set to, for example, 1 to 5 parts by weight relative to 100 parts by weight of the acrylic polymer.
作为交联剂，优选将异氰酸酯系交联剂与环氧系交联剂组合使用。通过将上述量的异氰酸酯系交联剂与上述量的环氧系交联剂组合使用，能够以高水平兼顾对被粘物以及基材层的粘附性和凝聚力。由此，能够实现显示良好的保持性能(粘合剂层的凝聚力)的粘合片。As the crosslinking agent, it is preferred to use an isocyanate crosslinking agent in combination with an epoxy crosslinking agent. By using the above amount of isocyanate crosslinking agent in combination with the above amount of epoxy crosslinking agent, it is possible to take into account both the adhesion to the adherend and the substrate layer and the cohesive force at a high level. Thus, it is possible to achieve an adhesive sheet showing good retention performance (cohesive force of the adhesive layer).
作为氮丙啶系交联剂的实例，例如可列举出：三羟甲基丙烷三[3-(1-氮丙啶基)丙酸酯]、三羟甲基丙烷三[3-(1-(2-甲基)氮丙啶基丙酸酯)]。作为氮丙啶系交联剂，可以使用市售品。例如可使用Chemitite PZ-33、Chemitite DZ-22E等Chemitite系列(NipponShokubai Co.,Ltd.制)等。Examples of aziridine crosslinking agents include trimethylolpropane tris[3-(1-aziridinyl)propionate] and trimethylolpropane tris[3-(1-(2-methyl)aziridinylpropionate)]. Commercially available aziridine crosslinking agents can be used. For example, Chemitite series (manufactured by Nippon Shokubai Co., Ltd.) such as Chemitite PZ-33 and Chemitite DZ-22E can be used.
作为三聚氰胺系交联剂的实例，可列举出：六羟甲基三聚氰胺、丁基化三聚氰胺树脂(例如，可以从DIC株式会社获得的商品名“SUPER BECKAMINE J-820-60N”)等。Examples of the melamine-based crosslinking agent include hexamethylolmelamine and butylated melamine resins (for example, trade name "SUPER BECKAMINE J-820-60N" available from DIC Corporation).
作为金属螯合物系交联剂的实例，例如可列举出：铝螯合物系化合物、钛螯合物系化合物、锌螯合物系化合物、锆螯合物系化合物、铁螯合物系化合物、钴螯合物系化合物、镍螯合物系化合物、锡螯合物系化合物、锰螯合物系化合物、铬螯合物系化合物等。Examples of the metal chelate crosslinking agent include aluminum chelate compounds, titanium chelate compounds, zinc chelate compounds, zirconium chelate compounds, iron chelate compounds, cobalt chelate compounds, nickel chelate compounds, tin chelate compounds, manganese chelate compounds, and chromium chelate compounds.
关于交联剂的含量，相对于丙烯酸系聚合物100重量份，优选含有0.01～10重量份，更优选含有0.1～5重量份。含量不足0.01重量份的情况下，存在丙烯酸系粘合剂的内聚力变小、粘接可靠性差的情况。另一方面，含量超过10重量份的情况下，存在丙烯酸系粘合剂的内聚力大、流动性降低、经时的粘合力上升不良的情况。The content of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the acrylic polymer. When the content is less than 0.01 parts by weight, the cohesive force of the acrylic adhesive is reduced, and the bonding reliability is poor. On the other hand, when the content exceeds 10 parts by weight, the cohesive force of the acrylic adhesive is large, the fluidity is reduced, and the adhesion strength increase over time is poor.
为了更有效地进行上述交联反应，也可以使用交联催化剂。作为交联催化剂，例如可以优选使用锡系催化剂(例如二月桂酸二辛基锡)。交联催化剂的使用量没有特别限制，例如相对于丙烯酸系聚合物100重量份，优选为0.0001～1重量份。In order to more effectively carry out the above crosslinking reaction, a crosslinking catalyst may also be used. As the crosslinking catalyst, for example, a tin catalyst (for example, dioctyltin dilaurate) may be preferably used. The amount of the crosslinking catalyst used is not particularly limited, and for example, it is preferably 0.0001 to 1 part by weight relative to 100 parts by weight of the acrylic polymer.
在此处公开的粘合剂层中，除了上述各成分以外，可以根据需要含有流平剂、交联助剂、增塑剂、软化剂、抗静电剂、防老剂、抗氧化剂等粘合剂领域中通常的各种添加剂。关于这样的各种添加剂，可以通过常规方法使用现有公知的添加剂。In the adhesive layer disclosed herein, in addition to the above-mentioned components, various additives commonly used in the adhesive field such as leveling agents, crosslinking aids, plasticizers, softeners, antistatic agents, antioxidants, and antioxidants may be contained as needed. Regarding such various additives, conventionally known additives may be used by conventional methods.
(第一粘合剂层的形成)(Formation of First Adhesive Layer)
在此公开的第一粘合剂层可以通过现有公知的方法来形成。例如可以采用通过将丙烯酸系粘合剂(粘合剂组合物)直接施加(典型地为涂布)到该基材层上并使其干燥而形成粘合剂层的方法(直接法)。另外，也可以采用通过将丙烯酸系粘合剂(粘合剂组合物)施加到具有剥离性的表面(剥离面)上并使其干燥而在该表面上形成粘合剂层、并将该粘合剂层转印到基材层上的方法(转印法)。从生产率的观点考虑，优选转印法。作为上述剥离面，可以利用剥离衬垫的表面、进行了剥离处理的基材层背面等。需要说明的是，在此公开的粘合剂层典型地是连续地形成，但并不限定于这样的形态，也可以为形成为例如点状、条纹状等规则或不规则图案的粘合剂层。The first adhesive layer disclosed herein can be formed by existing known methods.For example, the method (direct method) of forming adhesive layer by directly applying (typically coating) acrylic adhesive (adhesive composition) to the substrate layer and drying it can be adopted. In addition, the method (transfer method) of forming adhesive layer on the surface and transferring the adhesive layer to the substrate layer by applying acrylic adhesive (adhesive composition) to the surface (peeling surface) with peelability and drying it can also be adopted. From the viewpoint of productivity, the transfer method is preferred. As the above-mentioned peeling surface, the surface of the peeling liner, the back side of the substrate layer that has been peeled off, etc. can be utilized. It should be noted that the adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form, and can also be the adhesive layer formed into the regular or irregular pattern such as dot-shaped, stripe-shaped, etc.
粘合剂组合物的涂布例如可以使用凹版辊涂布机、模涂布机、棒涂布机等现有公知的涂布机来进行。或者，也可以通过浸渗或帘涂法等涂布粘合剂组合物。The adhesive composition can be applied using a conventionally known coater such as a gravure roll coater, a die coater, or a bar coater. Alternatively, the adhesive composition can be applied by impregnation or curtain coating.
从促进交联反应、提高制造效率等观点考虑，粘合剂组合物的干燥优选在加热下进行。干燥温度例如可以设定为40～150℃左右，通常优选设定为60～130℃左右。在使粘合剂组合物干燥后，出于粘合剂层内的成分迁移的调节、交联反应的进行、可能存在于基材膜或粘合剂层内的应变的松弛等目的，可以进一步进行老化。From the viewpoint of promoting the crosslinking reaction and improving the manufacturing efficiency, the drying of the adhesive composition is preferably carried out under heating. The drying temperature can be set to about 40 to 150° C., for example, and is usually preferably set to about 60 to 130° C. After the adhesive composition is dried, it can be further aged for the purpose of regulating the migration of components in the adhesive layer, carrying out the crosslinking reaction, and relaxing the strain that may exist in the substrate film or the adhesive layer.
第一粘合剂层的厚度没有特别限制，优选为5～50μm，更优选为15～40μm。通过将第一粘合剂层的厚度设为上述范围，可以实现良好的粘接性。第一粘合剂层的厚度不足5μm时，存在经时的粘合力上升不良的情况。另一方面，第一粘合剂层的厚度超过50μm时，存在贴合之后的粘合力的抑制效果变得不充分的情况。The thickness of the first adhesive layer is not particularly limited, and is preferably 5 to 50 μm, and more preferably 15 to 40 μm. By setting the thickness of the first adhesive layer to the above range, good adhesion can be achieved. When the thickness of the first adhesive layer is less than 5 μm, there is a situation where the adhesive force increases poorly over time. On the other hand, when the thickness of the first adhesive layer exceeds 50 μm, there is a situation where the inhibitory effect of the adhesive force after lamination becomes insufficient.
(第一粘合剂层的特性)(Characteristics of the First Adhesive Layer)
第一粘合剂层在100～150℃、优选130℃下加热3～10分钟后相对于不锈钢板的180°剥离粘合力N2与第一粘合剂层在20～25℃、优选23℃下相对于不锈钢板的180°剥离粘合力N1之比，即N2/N1≤2，优选N2/N1≤1.5。通过将上述N2/N1设在上述范围内，本发明的压敏粘合片不存在由于树脂包封时的压力，芯片不被所述压敏粘合片支持并且偏移离指定位置的缺点，并且压敏粘合片可以在封装体不破损的情况下被剥离，包封后对于包封树脂不发生残胶。当N2/N1超过2时，由于包封树脂的固化和热，压敏粘合片变得强烈地粘合至芯片面或包封树脂面，从而引起剥离所述粘合片时封装体的破损。180°剥离粘合力试验根据后述实施例中记载的方法、条件进行测定。The ratio of the 180° peel adhesion N2 of the first adhesive layer relative to the stainless steel plate after heating at 100-150°C, preferably 130°C for 3-10 minutes to the 180° peel adhesion N1 of the first adhesive layer relative to the stainless steel plate at 20-25°C, preferably 23°C, that is, N2/N1≤2, preferably N2/N1≤1.5. By setting the above-mentioned N2/N1 within the above-mentioned range, the pressure-sensitive adhesive sheet of the present invention does not have the disadvantage that the chip is not supported by the pressure-sensitive adhesive sheet and is offset from the specified position due to the pressure during resin encapsulation, and the pressure-sensitive adhesive sheet can be peeled off without damaging the package, and no residual adhesive will occur to the encapsulation resin after encapsulation. When N2/N1 exceeds 2, due to the curing and heat of the encapsulation resin, the pressure-sensitive adhesive sheet becomes strongly bonded to the chip surface or the encapsulation resin surface, thereby causing damage to the package when the adhesive sheet is peeled off. The 180° peel adhesion test is measured according to the method and conditions described in the embodiments described later.
本发明中的第一粘合剂层在20～25℃、优选23℃下相对于不锈钢板的180°剥离粘合力N1优选为0.1～3.0N/20mm，更优选为0.4～2.0N/20mm。通过使第一粘合剂层在20～25℃、优选23℃下相对于不锈钢板的180°剥离粘合力N1在上述范围内，粘合片具备充分的粘合力。当上述180°剥离粘合力N1小于0.1N/20mm时，对芯片的粘合性变得不充分，在操作期间剥离以及树脂包封期间的压力发生芯片位置的偏移。当上述180°剥离粘合力N1超过3.0N/20mm时，粘合剂层难以从芯片剥落，剥离操作性差，由于剥离工序带来封装体的损伤。The first adhesive layer in the present invention preferably has a 180° peel adhesion N1 relative to the stainless steel plate at 20 to 25°C, preferably at 23°C, of 0.1 to 3.0 N/20mm, and more preferably 0.4 to 2.0 N/20mm. By making the 180° peel adhesion N1 of the first adhesive layer relative to the stainless steel plate at 20 to 25°C, preferably at 23°C within the above range, the adhesive sheet has sufficient adhesion. When the above 180° peel adhesion N1 is less than 0.1 N/20mm, the adhesion to the chip becomes insufficient, and the chip position shifts due to the pressure during peeling during operation and during resin encapsulation. When the above 180° peel adhesion N1 exceeds 3.0 N/20mm, the adhesive layer is difficult to peel off from the chip, the peeling operability is poor, and the package is damaged due to the peeling process.
本发明中的第一粘合剂层在100～150℃、优选130℃下加热3～10分钟后相对于不锈钢板的180°剥离粘合力N2优选为0.2～6.0N/20mm，更优选为0.5～3.0N/20mm。通过上述在100～150℃、优选130℃下加热3～10分钟后的180°剥离粘合力N2在上述范围内，本发明的压敏粘合片在粘贴到被粘物上时经时后的胶粘可靠性优良，压敏粘合片可在不损坏封装体的情况下剥离，包封后对于包封树脂不发生残胶。The first adhesive layer in the present invention preferably has a 180° peeling adhesion N2 with respect to the stainless steel plate after heating at 100 to 150°C, preferably 130°C for 3 to 10 minutes of 0.2 to 6.0 N/20mm, more preferably 0.5 to 3.0 N/20mm. By having the 180° peeling adhesion N2 after heating at 100 to 150°C, preferably 130°C for 3 to 10 minutes within the above range, the pressure-sensitive adhesive sheet of the present invention has excellent adhesion reliability after time when attached to an adherend, and the pressure-sensitive adhesive sheet can be peeled without damaging the package body, and no residual adhesive will occur to the encapsulation resin after encapsulation.
当上述180°剥离粘合力N2小于0.2N/20mm时，对芯片的粘合性不充分，在操作期间剥离以及树脂包封期间的压力发生芯片位置的偏移。当上述180°剥离粘合力N2超过6.0N/20mm时，由于包封树脂的固化和加热，压敏粘合带强烈地粘合至芯片面，导致在将带剥离时封装体的破损，包封后对于包封树脂发生残胶。When the 180° peeling adhesion N2 is less than 0.2N/20mm, the adhesion to the chip is insufficient, and the chip position is shifted by the pressure during peeling during operation and during resin encapsulation. When the 180° peeling adhesion N2 exceeds 6.0N/20mm, the pressure-sensitive adhesive tape is strongly adhered to the chip surface due to the curing and heating of the encapsulating resin, resulting in damage to the package when the tape is peeled off, and residual adhesive to the encapsulating resin after encapsulation.
第一粘合剂层的凝胶率优选大于70％，更优选大于80％。当第一粘合剂层的凝胶率在上述范围内时，能够获得优异的粘合特性，当用树脂包封时晶片不偏移，并且对于包封树脂不发生残胶。第一粘合剂层的凝胶率例如可以根据丙烯酸系聚合物的组成、分子量、交联剂的使用的有无及其种类以及用量的选择等来调节。The gel fraction of the first adhesive layer is preferably greater than 70%, more preferably greater than 80%. When the gel fraction of the first adhesive layer is within the above range, excellent adhesive properties can be obtained, the wafer does not shift when encapsulated with a resin, and no residual adhesive occurs for the encapsulating resin. The gel fraction of the first adhesive layer can be adjusted, for example, according to the composition and molecular weight of the acrylic polymer, the presence or absence of a crosslinking agent, the type of crosslinking agent, and the amount of crosslinking agent.
粘合剂层的凝胶率如下求出。首先，从粘合剂层采集样品，测定该样品的重量，将该重量作为“W1”。接着，用四氟乙烯树脂制多孔膜将该样品包成荷包状，用风筝线捆住其口，得到包裹。接着，将该包裹浸渍到乙酸乙酯中，在室温(典型地为23℃)下静置7天。接着，从乙酸乙酯中回收包裹，将所回收的包裹在130℃干燥2小时。干燥后，测定该包裹的重量，由包裹的重量除去四氟乙烯树脂制多孔膜的重量和风筝线的重量而求出样品的重量，将该重量作为“W2”。然后，通过下式求出凝胶率。The gel fraction of the adhesive layer is calculated as follows. First, collect a sample from the adhesive layer, measure the weight of the sample, and refer to this weight as "W1". Next, wrap the sample into a purse shape with a porous membrane made of tetrafluoroethylene resin, and tie its mouth with a kite string to obtain a package. Next, immerse the package in ethyl acetate and let it stand at room temperature (typically 23°C) for 7 days. Next, recover the package from ethyl acetate, and dry the recovered package at 130°C for 2 hours. After drying, measure the weight of the package, and determine the weight of the sample by subtracting the weight of the porous membrane made of tetrafluoroethylene resin and the weight of the kite string from the weight of the package, and refer to this weight as "W2". Then, the gel fraction is calculated by the following formula.
凝胶率(质量％)＝(W2)/(W1)×100Gel fraction (mass %) = (W2)/(W1)×100
第一粘合剂层在20～25℃、优选23℃下的储能模量G'为0.5×105～12×105Pa，优选2×105～9×105Pa。当第一粘合剂层在20～25℃、优选23℃下的储能模量G'在上述范围内时，可降低由于当将芯片粘合至压敏粘合片时以及当用树脂包封芯片时的压力导致的芯片嵌入粘合剂层，并且可以降低伴随嵌入的芯片面相对于包封树脂面变得突出的位置差异(偏离)。在本发明中，储能模量G'可以通过动态机械分析仪(DMA)进行测定。The storage modulus G' of the first adhesive layer at 20 to 25°C, preferably 23°C, is 0.5×105 to 12×105 Pa, preferably 2×105 to 9×105 Pa. When the storage modulus G' of the first adhesive layer at 20 to 25°C, preferably 23°C, is within the above range, the chip embedding into the adhesive layer due to the pressure when the chip is bonded to the pressure-sensitive adhesive sheet and when the chip is encapsulated with a resin can be reduced, and the position difference (deviation) of the chip surface protruding relative to the encapsulating resin surface accompanying the embedding can be reduced. In the present invention, the storage modulus G' can be measured by a dynamic mechanical analyzer (DMA).
第一粘合剂层的储能模量G'例如可以通过构成第一粘合剂层中的粘合剂的树脂的种类(即该树脂的玻璃化转变温度、分子量等)而进行控制。构成第一粘合剂层中的粘合剂的树脂的玻璃化转变温度例如可以适当地选择构成该树脂的单体来进行调节。The storage modulus G' of the first adhesive layer can be controlled, for example, by the type of resin constituting the adhesive in the first adhesive layer (i.e., the glass transition temperature, molecular weight, etc. of the resin). The glass transition temperature of the resin constituting the adhesive in the first adhesive layer can be adjusted, for example, by appropriately selecting the monomer constituting the resin.
<第二粘合剂层><Second Adhesive Layer>
在一个优选的实施方式中，如图7所示，本发明的半导体器件生产用耐热性压敏粘合片还包括第二粘合剂层13，该第二粘合剂层13设置在基材层的与第一粘合剂层相反的一侧。In a preferred embodiment, as shown in FIG. 7 , the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention further includes a second adhesive layer 13 provided on the side of the substrate layer opposite to the first adhesive layer.
作为构成第二粘合剂层的粘合剂，例如可列举出有机硅系粘合剂、包括丙烯酸系聚合物作为基础聚合物的丙烯酸系粘合剂、包括天然橡胶或合成橡胶作为基础聚合物的橡胶系粘合剂、苯乙烯/共轭二烯嵌段共聚物系粘合剂、聚酯系粘合剂、聚酰胺系粘合剂等。其中，从耐热性的观点，优选使用有机硅系粘合剂和丙烯酸系粘合剂，更优选使用有机硅系粘合剂。Examples of the adhesive constituting the second adhesive layer include silicone adhesives, acrylic adhesives containing acrylic polymers as base polymers, rubber adhesives containing natural rubber or synthetic rubber as base polymers, styrene/conjugated diene block copolymer adhesives, polyester adhesives, polyamide adhesives, etc. Among them, silicone adhesives and acrylic adhesives are preferably used, and silicone adhesives are more preferably used, from the viewpoint of heat resistance.
作为上述有机硅系粘合剂，优选使用例如将包含有机聚硅氧烷的有机硅橡胶或者有机硅树脂等作为基础聚合物的有机硅系粘合剂。作为构成有机硅系粘合剂的基础聚合物，也可以使用将上述有机硅橡胶或者有机硅树脂交联而得到的基础聚合物。As the silicone adhesive, for example, silicone rubber or silicone resin containing organopolysiloxane is preferably used as a base polymer. As the base polymer constituting the silicone adhesive, a base polymer obtained by crosslinking the silicone rubber or silicone resin can also be used.
作为上述丙烯酸系粘合剂，可以使用任意的适当丙烯酸系粘合剂。可列举出例如以丙烯酸系聚合物(均聚物或共聚物)作为基础聚合物的丙烯酸系粘合剂等，所述丙烯酸系聚合物使用1种或2种以上的(甲基)丙烯酸烷基酯作为单体成分。在一个实施方式中，可以使用上述第一粘合剂层中说明的丙烯酸系粘合剂，在此不再详细描述。As the acrylic adhesive, any appropriate acrylic adhesive can be used. For example, an acrylic adhesive using an acrylic polymer (homopolymer or copolymer) as a base polymer, wherein the acrylic polymer uses one or more (meth) alkyl esters as monomer components, can be cited. In one embodiment, the acrylic adhesive described in the first adhesive layer can be used, which will not be described in detail here.
作为上述橡胶系粘合剂，可列举出例如以下述橡胶作为基础聚合物的橡胶系粘合剂，所述橡胶为：天然橡胶；聚异戊二烯橡胶、苯乙烯·丁二烯(SB)橡胶、苯乙烯·异戊二烯(SI)橡胶、苯乙烯·异戊二烯·苯乙烯嵌段共聚物(SIS)橡胶、苯乙烯·丁二烯·苯乙烯嵌段共聚物(SBS)橡胶、苯乙烯·乙烯·丁烯·苯乙烯嵌段共聚物(SEBS)橡胶、苯乙烯·乙烯·丙烯·苯乙烯嵌段共聚物(SEPS)橡胶、苯乙烯·乙烯·丙烯嵌段共聚物(SEP)橡胶、再生橡胶、丁基橡胶、聚异丁烯、它们的改性体等合成橡胶等。Examples of the rubber-based adhesive include rubber-based adhesives having the following rubbers as base polymers: natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, synthetic rubbers such as their modified forms, and the like.
第二粘合剂层和第一粘合剂层的组成和构成可以相同，或者组成和构成的一者或两者可以不同。作为第二粘合剂层与第一粘合剂层的组成相同且构成不同的方式的例子，可列举出第一粘合剂层和第二粘合剂层为由相同组成的粘合剂组合物构成的厚度不同的粘合剂层的方式。The second adhesive layer and the first adhesive layer may have the same composition and structure, or one or both of the composition and structure may be different. As an example of a mode in which the second adhesive layer and the first adhesive layer have the same composition and different structure, the first adhesive layer and the second adhesive layer are adhesive layers of different thicknesses composed of an adhesive composition of the same composition.
对于第二粘合剂层中使用的粘合剂而言，优选粘合剂的可溶性部分的重均分子量(Mw)为2,000～6,000。重均分子量小于2,000时，具有粘合剂层的凝聚力降低的倾向，有时在被粘物的固定时发生偏移，或者剥离时产生残胶。另一方面，重均分子量超过6,000时，具有凝聚力因聚合物的缠结带来的效果而增大从而流动性降低的倾向，有时不能得到足够的粘合面积而无法进行被粘物的固定。For the adhesive used in the second adhesive layer, the weight average molecular weight (Mw) of the soluble part of the adhesive is preferably 2,000 to 6,000. When the weight average molecular weight is less than 2,000, the cohesive force of the adhesive layer tends to be reduced, and sometimes the adherend is offset when fixed, or residual adhesive is generated when peeled. On the other hand, when the weight average molecular weight exceeds 6,000, the cohesive force tends to increase due to the effect of entanglement of the polymer, thereby reducing the fluidity, and sometimes it is not possible to obtain a sufficient bonding area and fix the adherend.
在第二粘合剂层中，从粘合特性(粘接力、粘性、耐久性、保持特性)的平衡方面出发，凝胶率优选为40～90％，优选为50～85％。当不足40％时，可能会出现内聚力不足，导致剥离时发生内聚破坏，部分粘合剂残留在被粘体表面，发生加工性降低的情况。另一方面，当超过90％时，可能会出现粘性不足，达不到粘接要求，发生粘接可靠性降低的情况。第二粘合剂层的凝胶率例如可以根据粘合剂的组成、分子量、交联剂的使用的有无及其种类以及用量的选择等来调节。In the second adhesive layer, from the perspective of balancing the adhesive properties (adhesive force, viscosity, durability, and retention properties), the gel fraction is preferably 40 to 90%, and preferably 50 to 85%. When it is less than 40%, insufficient cohesion may occur, resulting in cohesive failure during peeling, and part of the adhesive may remain on the surface of the adherend, resulting in reduced processability. On the other hand, when it exceeds 90%, insufficient viscosity may occur, failing to meet the bonding requirements, resulting in reduced bonding reliability. The gel fraction of the second adhesive layer can be adjusted, for example, based on the composition of the adhesive, molecular weight, the presence or absence of a cross-linking agent, its type, and the amount of the cross-linking agent.
第二粘合剂层在20～25℃、优选23℃下相对于不锈钢板的15°剥离粘合力为2～100N/20mm，优选为2～50N/20mm。通过将上述15°剥离粘合力设为这样的范围，可使压敏粘合片具备充分的粘合力，并且能够容易地进行使用后的剥离。当上述15°剥离粘合力小于2N/20mm时，有可能在剥离工序以外被容易地剥离。另一方面，当上述15°剥离粘合力超过100N/20mm时，有可能在不需要时的剥离作业性差，因剥离作业而损坏被粘物等。The second adhesive layer has a 15° peeling adhesion of 2 to 100 N/20 mm, preferably 2 to 50 N/20 mm, relative to the stainless steel plate at 20 to 25° C., preferably at 23° C. By setting the 15° peeling adhesion to such a range, the pressure-sensitive adhesive sheet can have sufficient adhesion and can be easily peeled off after use. When the 15° peeling adhesion is less than 2 N/20 mm, it is possible to be easily peeled off outside the peeling process. On the other hand, when the 15° peeling adhesion exceeds 100 N/20 mm, the peeling workability may be poor when it is not necessary, and the adherend may be damaged due to the peeling operation.
第二粘合剂层在150℃下加热4小时后相对于不锈钢板的15°剥离粘合力为3～130N/20mm，优选为3～100N/20mm。通过将上述15°剥离粘合力设为这样的范围，将压敏粘合片在粘贴到被粘物上时经时后的胶粘可靠性优良，并且能够容易地进行使用后的剥离。当上述15°剥离粘合力小于3N/20mm时，对被粘物的粘合性不充分。另一方面，当上述15°剥离粘合力超过130N/20mm时，剥离作业性差，从而造成被粘物的破损，或者产生残胶污染。The second adhesive layer has a 15° peeling adhesion of 3 to 130 N/20 mm, preferably 3 to 100 N/20 mm, relative to a stainless steel plate after being heated at 150°C for 4 hours. By setting the 15° peeling adhesion to such a range, the pressure-sensitive adhesive sheet has excellent adhesion reliability after being attached to an adherend over time, and can be easily peeled off after use. When the 15° peeling adhesion is less than 3 N/20 mm, the adhesion to the adherend is insufficient. On the other hand, when the 15° peeling adhesion exceeds 130 N/20 mm, the peeling workability is poor, resulting in damage to the adherend or residual adhesive contamination.
第二粘合剂层在20～25℃、优选23℃下的储能模量G'为0.8×105～2.5×105Pa，优选1×105～2.5×105Pa。通过将23℃下的储能模量G'设为上述范围内，第二粘合剂层可以保持加工性或操作性等所需要的凝聚力，并且可以确保将第二粘合剂层与被粘物贴合时的初始粘合性。The storage modulus G' of the second adhesive layer at 20 to 25°C, preferably at 23°C, is 0.8×105 to 2.5×105 Pa, preferably 1×105 to 2.5×105 Pa. By setting the storage modulus G' at 23°C within the above range, the second adhesive layer can maintain the cohesive force required for processability and handling, and can ensure initial adhesion when the second adhesive layer is attached to an adherend.
第二粘合剂层在150℃下的储能模量G'为0.5×105～1.6×105Pa。通过将150℃下的储能模量G'设为上述范围内，可以得到粘合力与剥离性均衡优异的粘合片。The storage modulus G' of the second pressure-sensitive adhesive layer at 150°C is 0.5×105 to 1.6×105 Pa. When the storage modulus G' at 150°C is within the above range, a pressure-sensitive adhesive sheet having an excellent balance between pressure-sensitive adhesive force and releasability can be obtained.
第二粘合剂层的储能模量G'例如可以通过构成第二粘合剂层中的粘合剂的树脂的种类(即该树脂的玻璃化转变温度、分子量等)而进行控制。构成第二粘合剂层中的粘合剂的树脂的玻璃化转变温度例如可以适当地选择构成该树脂的单体来进行调节。在本发明中储能模量G'可以通过动态机械分析仪(DMA)进行测定。The storage modulus G' of the second adhesive layer can be controlled, for example, by the type of resin constituting the adhesive in the second adhesive layer (i.e., the glass transition temperature, molecular weight, etc. of the resin). The glass transition temperature of the resin constituting the adhesive in the second adhesive layer can be adjusted, for example, by appropriately selecting the monomer constituting the resin. In the present invention, the storage modulus G' can be measured by a dynamic mechanical analyzer (DMA).
第二粘合剂层的厚度没有特别限制，优选为5～50μm，更优选为10～40μm。通过将第二粘合剂层的厚度设为上述范围，可以实现良好的粘接性。第二粘合剂层的厚度不足5μm时，存在经时的粘合力上升不良的情况。另一方面，第二粘合剂层的厚度超过50μm时，存在贴合之后的粘合力的抑制效果变得不充分的情况。The thickness of the second adhesive layer is not particularly limited, and is preferably 5 to 50 μm, and more preferably 10 to 40 μm. By setting the thickness of the second adhesive layer to the above range, good adhesion can be achieved. When the thickness of the second adhesive layer is less than 5 μm, there is a situation where the adhesive force increases poorly over time. On the other hand, when the thickness of the second adhesive layer exceeds 50 μm, there is a situation where the inhibitory effect of the adhesive force after lamination becomes insufficient.
(离型膜)(Release film)
本发明的半导体器件生产用耐热性压敏粘合片根据需要可以进一步具备离型膜。离型膜为包括基材膜和形成于其一侧上的剥离剂层的片，并且是为了在使用本发明的半导体器件生产用耐热性压敏粘合片之前露出粘合剂层的各个面而剥离的片。在本发明中，如图7所示，半导体器件生产用耐热性压敏粘合片包括第一离型膜10和第二离型膜14。第一离型膜10设置在第一粘合剂层12的与基材层11相反的一侧，第二离型膜14设置在第二粘合剂层13的与基材层11相反的一侧。The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention may further be provided with a release film as required. The release film is a sheet including a substrate film and a release agent layer formed on one side thereof, and is a sheet peeled off in order to expose the various faces of the adhesive layer before using the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention. In the present invention, as shown in FIG7 , the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production includes a first release film 10 and a second release film 14. The first release film 10 is arranged on the side of the first adhesive layer 12 opposite to the substrate layer 11, and the second release film 14 is arranged on the side of the second adhesive layer 13 opposite to the substrate layer 11.
剥离剂层可通过以下来获得：根据要与其接触的粘合剂，从常规剥离剂层如长链烷基类、氟树脂类和硅酮树脂类中适当地选择。The release agent layer can be obtained by appropriately selecting from conventional release agent layers such as long-chain alkyl type, fluorine resin type, and silicone resin type according to the adhesive to be brought into contact therewith.
作为基材膜，可使用常规膜，并可选自，例如，塑料膜如聚醚醚酮、聚醚酰亚胺、多芳基化合物、聚萘二甲酸乙二酯、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、聚氯乙烯共聚物膜、聚对苯二甲酸乙二酯膜、聚对苯二甲酸丁二酯膜、聚氨酯膜、乙烯-乙酸乙烯酯共聚物膜、离子键树脂膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚苯乙烯薄膜和聚碳酸酯膜。As the substrate film, conventional films can be used and can be selected from, for example, plastic films such as polyetheretherketone, polyetherimide, polyarylate, polyethylene naphthalate, polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, polyvinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, ionomer resin film, ethylene-(meth)acrylic acid copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film and polycarbonate film.
根据粘合剂层的树脂，可使用的剥离剂层为包含选自如下的剥离剂的层：常规剥离剂如氟化硅酮树脂类剥离剂、氟树脂类剥离剂、硅酮树脂类剥离剂、聚乙烯醇树脂、聚丙烯树脂以及长链烷基化合物。Depending on the resin of the adhesive layer, a release agent layer that can be used is a layer containing a release agent selected from conventional release agents such as fluorinated silicone resin-based release agents, fluororesin-based release agents, silicone resin-based release agents, polyvinyl alcohol resins, polypropylene resins, and long-chain alkyl compounds.
<半导体器件生产用耐热性压敏粘合片的生产方法><Method for producing heat-resistant pressure-sensitive adhesive sheet for semiconductor device production>
本发明的半导体器件生产用耐热性压敏粘合片可通过一般生产方法生产。例如，将用于构成第一粘合剂层，以及如果需要的第二粘合剂层的组合物溶于给定的溶剂以制备涂布液，将涂布液施涂至基材层以便获得目标半导体器件生产用耐热性压敏粘合片的层结构，然后在给定条件下将所得涂布层加热并干燥。The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention can be produced by a general production method. For example, a composition for constituting the first adhesive layer and, if necessary, the second adhesive layer is dissolved in a given solvent to prepare a coating liquid, the coating liquid is applied to a substrate layer to obtain a layer structure of the target heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, and then the resulting coating layer is heated and dried under given conditions.
此外，单一膜可以通过例如，将用于构成第一粘合剂层、第二粘合剂层等的组合物的各溶液流延在可剥离膜等上来制备，并且那些膜可以依次层压在基材层上。可组合涂布液的施涂和由单一膜的层压。所使用的溶剂不特别限定。考虑到用于构成粘合剂层的材料的良好溶解性的需要，优选使用酮类溶剂如甲基乙基酮。还可使用以下形成半导体器件生产用压敏粘合片的方法：将粘合剂层的构成材料制成水性分散溶液，将该溶液施涂至基材层，加热并干燥所得涂布层，重复那些步骤，从而层压粘合剂层。In addition, single film can be prepared by, for example, casting each solution of the composition for constituting the first adhesive layer, the second adhesive layer, etc. on a peelable film, etc., and those films can be laminated on the substrate layer in sequence. The application of the coating solution can be combined and the lamination by the single film. The solvent used is not particularly limited. Considering the needs for the good solubility of the material constituting the adhesive layer, it is preferred to use ketone solvents such as methyl ethyl ketone. The following method for forming a pressure-sensitive adhesive sheet for semiconductor device production can also be used: the constituent material of the adhesive layer is made into an aqueous dispersion solution, the solution is applied to the substrate layer, heated and dried the resulting coating layer, and those steps are repeated, thereby the laminated adhesive layer.
<使用半导体器件生产用耐热性压敏粘合片的方法><Method of using heat-resistant pressure-sensitive adhesive sheet for semiconductor device production>
将半导体器件生产用耐热性压敏粘合片用于图1和图2A至2F等中所示的步骤。The heat-resistant pressure-sensitive adhesive sheet for semiconductor device production is used in the steps shown in FIG. 1 and FIGS. 2A to 2F and the like.
作为实例，以下描述用于生产无基板BGA的方法的概要。As an example, an outline of a method for producing a substrate-less BGA is described below.
图1为示出其中用树脂包封无基板半导体芯片的半导体器件的生产方法的图，该方法采用本发明的半导体器件生产用耐热性压敏粘合片。FIG. 1 is a diagram showing a method for producing a semiconductor device in which a substrate-less semiconductor chip is encapsulated with a resin, the method using the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention.
在步骤(a)中，将本发明的半导体器件生产用耐热性压敏粘合片2粘合并固定至基板3。在步骤(b)中，将半导体芯片以任意的间隔粘合并固定至该片。在随后的步骤(c)中，用包封树脂4包封已固定的半导体芯片以便嵌入芯片。In step (a), the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention is bonded and fixed to a substrate 3. In step (b), semiconductor chips are bonded and fixed to the sheet at arbitrary intervals. In the subsequent step (c), the fixed semiconductor chips are encapsulated with an encapsulating resin 4 so as to embed the chips.
在步骤(d)中，通过加热剥离将由此包封的多个芯片与包封树脂和半导体器件生产用耐热性压敏粘合片2一起从基板剥离。在步骤(e)中，将本发明的半导体器件生产用耐热性压敏粘合片2从树脂包封的半导体芯片剥离。In step (d), the plurality of chips thus encapsulated are peeled off from the substrate together with the encapsulating resin and the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production by thermal peeling. In step (e), the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention is peeled off from the resin-encapsulated semiconductor chips.
在步骤(f)中，将各种图案印刷施加于半导体芯片与半导体芯片表面之间的区域以形成布线用引线等。在随后的步骤(g)中，布线用引线形成作为芯片表面上的球形连接电极的凸块等。In step (f), various patterns are printed and applied to the semiconductor chip and the area between the semiconductor chip surface to form wiring leads, etc. In the subsequent step (g), the wiring leads are formed into bumps, etc., which are ball-shaped connection electrodes on the chip surface.
最终，在步骤(h)中，通过切割等将半导体芯片间的包封树脂部分切断，从而可获得装配有单独的半导体芯片的各半导体器件。Finally, in step (h), the encapsulating resin portions between the semiconductor chips are cut by dicing or the like, so that individual semiconductor devices equipped with individual semiconductor chips can be obtained.
以下参考图2A至2F具体描述无基板封装体的生产方法。The method for producing the substrate-less package is described in detail below with reference to FIGS. 2A to 2F .
(半导体芯片的粘合步骤)(Semiconductor chip bonding step)
通过粘合等将半导体器件生产用耐热性压敏粘合片2固定至基板3，并且在上面露出第一粘合剂层侧。The heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production is fixed to the substrate 3 by bonding or the like with the first adhesive layer side exposed thereon.
将要用树脂包封的给定的半导体芯片1放置于并粘合至第一粘合剂层以便获得给定的构造，从而将芯片1固定至半导体器件生产用耐热性压敏粘合片2的第一粘合剂层，如图2A所示。在该情况下，半导体芯片的结构、形状和尺寸等不特别限定。A given semiconductor chip 1 to be encapsulated with a resin is placed on and adhered to the first adhesive layer so as to obtain a given configuration, thereby fixing the chip 1 to the first adhesive layer of the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production, as shown in FIG. 2A . In this case, the structure, shape, size, etc. of the semiconductor chip are not particularly limited.
可选地，将多个芯片1粘合至在其两侧上均具有粘合剂层的半导体器件生产用耐热性压敏粘合片2，将该半导体器件生产用耐热性压敏粘合片2固定至基板3以形成如图2A所示的结构。Alternatively, a plurality of chips 1 are bonded to a heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production having adhesive layers on both sides thereof, and the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production is fixed to a substrate 3 to form a structure as shown in FIG. 2A .
(包封步骤)(Encapsulation Step)
用包封树脂4从具有图2A所示结构的芯片1上面包封所述芯片1以便集成多个芯片1从而形成图2B所示的结构。The chip 1 having the structure shown in FIG. 2A is encapsulated from above with an encapsulating resin 4 so as to integrate a plurality of chips 1 to form the structure shown in FIG. 2B .
用于其中使用本发明的半导体器件生产用耐热性压敏粘合片2的包封步骤的树脂可为常规包封树脂如环氧树脂。考虑到半导体器件生产用耐热性压敏粘合片2的耐热性，选择粉状树脂的熔融温度和固化温度以及液体树脂的固化温度。本发明的半导体器件生产用耐热性压敏粘合片2在普通包封树脂的熔融温度和固化温度下具有耐热性。The resin used for the encapsulation step in which the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention is used may be a conventional encapsulation resin such as an epoxy resin. The melting temperature and the curing temperature of the powdered resin and the curing temperature of the liquid resin are selected in consideration of the heat resistance of the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production. The heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention has heat resistance at the melting temperature and the curing temperature of the ordinary encapsulation resin.
为了保护芯片的目的，使用上述树脂在模具中进行包封步骤，并在例如170至180℃的温度下进行。For the purpose of protecting the chip, an encapsulation step is performed in a mold using the above-mentioned resin and is performed at a temperature of, for example, 170 to 180°C.
在剥离半导体器件生产用耐热性压敏粘合片2之后，进行后成型固化。After the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production is peeled off, post-molding curing is performed.
(剥离步骤)(Peeling step)
在固定于基板3上的半导体器件生产用耐热性压敏粘合片2的芯片1用树脂包封后，在如下条件下进行加热：200至250℃的温度下，1至90秒的时间(热板等)或1至15分钟的时间(热风干燥器)，以便解除在半导体器件生产用耐热性压敏粘合片2和基板3之间通过压敏粘合剂等的固定，半导体器件生产用耐热性压敏粘合片2和基板3彼此分开。After the chip 1 of the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production fixed on the substrate 3 is encapsulated with a resin, heating is performed under the following conditions: at a temperature of 200 to 250° C., for a time of 1 to 90 seconds (hot plate, etc.) or a time of 1 to 15 minutes (hot air dryer) to release the fixation between the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production and the substrate 3 by the pressure-sensitive adhesive, etc., and the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production and the substrate 3 are separated from each other.
其后，将半导体器件生产用耐热性压敏粘合片2从包括用树脂包封的芯片1的层剥离，如图2C所示。Thereafter, the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production is peeled from the layer including the chip 1 encapsulated with the resin, as shown in FIG. 2C .
可选地，还可使用以下方法：其中半导体器件生产用耐热性压敏粘合片2和基板3不彼此分离，并保持集成形式，将用包封树脂包封的多个芯片1从半导体器件生产用耐热性压敏粘合片2的压敏粘合剂层分离。Alternatively, a method may also be used in which the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production and the substrate 3 are not separated from each other and remain in an integrated form, and the plurality of chips 1 encapsulated with the encapsulating resin are separated from the pressure-sensitive adhesive layer of the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production.
(电极形成步骤)(Electrode Formation Step)
如图2D所示，在包括用树脂包封的芯片1的层的一侧，其上层压半导体器件生产用耐热性压敏粘合片2，并露出芯片1表面的一部分，通过如丝网印刷的方法使电极5形成于各芯片的给定区域上。所使用的电极材料可为常规材料。As shown in Fig. 2D, on one side of the layer including the chip 1 encapsulated with resin, a heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production is laminated thereon, and a part of the surface of the chip 1 is exposed, and an electrode 5 is formed on a given area of each chip by a method such as screen printing. The electrode material used can be a conventional material.
(切割步骤)(Cutting steps)
如图2E所示，将包括用树脂包封的芯片1的层固定于优选具有切割环7的切割带8，并使用用于普通切割步骤的切割刀6进行切割，从而获得如图2F所示的各自具有用树脂包封的多个芯片1的多个无基板封装体。As shown in Figure 2E, the layer including the chip 1 encapsulated with resin is fixed to a cutting tape 8 preferably having a cutting ring 7, and is cut using a cutting knife 6 used for a normal cutting step, thereby obtaining a plurality of substrate-free packages each having a plurality of chips 1 encapsulated with resin as shown in Figure 2F.
在该情况下，当各芯片1不定位于给定位置时，电极5的形成变得不精确，并且各封装体中芯片1的位置变得不精确。在最坏的情况下，存在当进行切割时切割刀6接触芯片1的可能性。In this case, when each chip 1 is not positioned at a given position, the formation of the electrode 5 becomes inaccurate, and the position of the chip 1 in each package becomes inaccurate. In the worst case, there is a possibility that the dicing blade 6 contacts the chip 1 when dicing.
当使用本发明的半导体器件生产用耐热性压敏粘合片2时，在用树脂的包封步骤中可防止芯片1的位置偏移。因此，切割步骤可在无此类问题的情况下平稳地进行，结果，可获得其中芯片1精确定位于包封树脂4的封装体。When the heat-resistant pressure-sensitive adhesive sheet 2 for semiconductor device production of the present invention is used, the positional deviation of the chip 1 can be prevented in the encapsulation step with the resin. Therefore, the dicing step can be smoothly performed without such a problem, and as a result, a package in which the chip 1 is accurately positioned in the encapsulation resin 4 can be obtained.
此外，在现有方法中，还存在以下情况：由于包封树脂的压力导致芯片不受半导体器件生产用耐热性压敏粘合片支持并且从指定位置偏移，或者因为包封树脂的压力过强、或半导体器件生产用耐热性压敏粘合片过软的原因、或因为那些组合原因，芯片嵌入半导体器件生产用耐热性压敏粘合片，如图3B所示。在此类情况中，令人担忧的是芯片不能完全用包封树脂包封，并且芯片从树脂表面突出以形成包封树脂面和芯片面之间产生位置差异的状态(偏离)。Furthermore, in the conventional method, there is also a case where the chip is not supported by the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production due to the pressure of the encapsulation resin and deviates from the specified position, or the chip is embedded in the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production because the pressure of the encapsulation resin is too strong, or the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production is too soft, or because of those combined reasons, as shown in FIG3B. In such a case, there is a concern that the chip cannot be completely encapsulated with the encapsulation resin, and the chip protrudes from the resin surface to form a state (deviation) in which a positional difference is generated between the encapsulation resin surface and the chip surface.
在芯片的一部分从树脂面突出的状态下，在随后所形成的电极的面的高度上发生偏移。因此，在将芯片连接到电路基板时，变得难以确定地将芯片连接到电路基板。When a part of the chip protrudes from the resin surface, a deviation occurs in the height of the surface of the electrode to be formed later. Therefore, when the chip is connected to the circuit substrate, it becomes difficult to connect the chip to the circuit substrate with certainty.
当使用本发明的半导体器件生产用耐热性压敏粘合片时，芯片不嵌入半导体器件生产用耐热性压敏粘合片，如图3A所示，芯片不从固化的包封树脂面突出，并且芯片之间电极的随后形成也确定地进行。此外，甚至在电路基板上设置封装体的情况下，各电极也可确定地连接到电路基板上的预定区域。When the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention is used, the chip is not embedded in the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, as shown in FIG3A, the chip does not protrude from the cured encapsulation resin surface, and the subsequent formation of electrodes between the chips is also surely performed. In addition, even in the case of providing a package body on a circuit substrate, each electrode can be surely connected to a predetermined area on the circuit substrate.
另外，在现有的用树脂包封期间，由于基材层和半导体器件生产用耐热性压敏粘合片的粘合剂层的膨胀和弹性，示于图4的(a)的半导体器件生产用耐热性压敏粘合片沿如图4的(b)所示的平面方向变形，从而设置于半导体器件生产用耐热性压敏粘合片上的芯片的位置在某些情况下会移动。此外，芯片有时可由于在封装用于包封的树脂时所引起的压力而移动。In addition, during the conventional encapsulation with resin, due to the expansion and elasticity of the adhesive layer of the substrate layer and the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production shown in FIG. 4 (a) is deformed in the plane direction as shown in FIG. 4 (b), so that the position of the chip set on the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production may move in some cases. In addition, the chip may sometimes move due to the pressure caused when the resin for encapsulation is packaged.
结果，在芯片上设置电极时，芯片和电极之间的相对位置关系与预定的位置关系不同。此外，在用树脂包封芯片并随后切割时，切割步骤中基于芯片的预定位置而提前确定的切割线与通过芯片的实际位置变得必要的切割线不同。As a result, when the electrode is set on the chip, the relative positional relationship between the chip and the electrode is different from the predetermined positional relationship. In addition, when the chip is encapsulated with resin and then cut, the cutting line determined in advance based on the predetermined position of the chip in the cutting step is different from the cutting line that becomes necessary through the actual position of the chip.
在此情况下，通过切割所获得的各封装体在包封芯片的位置产生偏移，随后的步骤不能平稳地进行。此外，可不期望地获得未充分包封的封装体。In this case, each package obtained by cutting has a deviation in the position of encapsulating the chip, and the subsequent steps cannot be smoothly performed. In addition, a package that is not fully encapsulated may be obtained undesirably.
在从用树脂包封的芯片剥离半导体器件生产用耐热性压敏粘合片时，特别取决于在半导体器件生产用耐热性压敏粘合片的芯片侧形成的压敏粘合剂的性质，由于包封树脂的固化和加热，粘合力变强，从而显示重剥离性。因此，令人担忧的是剥离变难，发生如图5所示的残胶，或者发生剥离带电。When peeling off the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production from the chip encapsulated with resin, depending on the properties of the pressure-sensitive adhesive formed on the chip side of the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, the adhesive force becomes strong due to the curing and heating of the encapsulating resin, thereby showing heavy peelability. Therefore, there is a concern that peeling becomes difficult, residual adhesive as shown in Figure 5 occurs, or peeling electrification occurs.
在剥离变难的情况下，剥离时间延长，导致生产性劣化。在发生如图5所示的残胶9的情况下，不能进行随后的步骤如电极的形成。此外，在产生剥离放电的情况下，由于灰尘等的附着在随后的步骤中可发生不利情况。When peeling becomes difficult, the peeling time is prolonged, resulting in deterioration of productivity. When residual adhesive 9 as shown in FIG. 5 occurs, subsequent steps such as electrode formation cannot be performed. In addition, when peeling discharge occurs, unfavorable conditions may occur in subsequent steps due to the attachment of dust, etc.
然而，当使用本发明的半导体器件生产用耐热性压敏粘合片时，切割步骤可在无上述问题的情况下平稳地进行，可获得芯片精确定位于包封树脂的封装体。并且，本发明的半导体器件生产用耐热性压敏粘合片能够在使用之后轻轻剥离，包封后对于包封树脂不发生残胶。However, when the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention is used, the dicing step can be smoothly performed without the above-mentioned problem, and a package in which the chip is accurately positioned in the encapsulation resin can be obtained. In addition, the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention can be easily peeled off after use, and no residual adhesive will occur to the encapsulation resin after encapsulation.
参考实施例更详细地描述本发明，但应注意，本发明不解释为受实施例限制。The present invention is described in more detail with reference to Examples, but it should be noted that the present invention is not construed as being limited to the Examples.
实施例Example
<粘合剂组合物的制备><Preparation of Adhesive Composition>
(例1)(Example 1)
向具备搅拌器、温度计、氮气导入管和回流冷凝器的反应容器中，投入丙烯酸正丁酯(BA)(浙江卫星制造)94重量份、丙烯酸(AA)1重量份、丙烯酸-2-羟基乙酯(HEA)(大阪有机制造)5重量份、及作为聚合溶剂的醋酸乙酯60重量份，在60～65℃下在氮气气氛下搅拌1小时后，作为热聚合引发剂投入2,2’-偶氮二异丁腈(AIBN)0.15份，在60～65℃下进行6小时反应，得到丙烯酸系聚合物A1的溶液。该丙烯酸系聚合物A1的Mw为64万。Into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 94 parts by weight of n-butyl acrylate (BA) (manufactured by Zhejiang Satellite), 1 part by weight of acrylic acid (AA), 5 parts by weight of 2-hydroxyethyl acrylate (HEA) (manufactured by Osaka Organic), and 60 parts by weight of ethyl acetate as a polymerization solvent were added, and stirred at 60 to 65° C. in a nitrogen atmosphere for 1 hour, and then 0.15 parts of 2,2'-azobisisobutyronitrile (AIBN) was added as a thermal polymerization initiator, and reacted at 60 to 65° C. for 6 hours to obtain a solution of acrylic polymer A1. The Mw of the acrylic polymer A1 was 640,000.
向上述丙烯酸系聚合物溶液中，相对于该溶液中所含的丙烯酸系聚合物100重量份，加入5重量份作为交联剂的异氰酸酯系交联剂(L 75(C)，科思创制造)和2重量份环氧系交联剂(T/C，美国CVC制造)，进行搅拌混合来制备粘合剂组合物C1。To the above-mentioned acrylic polymer solution, 5 parts by weight of an isocyanate crosslinking agent (L 75 (C), manufactured by Covestro) and 2 parts by weight of an epoxy crosslinking agent (T/C, manufactured by CVC, USA) as a crosslinking agent were added based on 100 parts by weight of the acrylic polymer contained in the solution, and the mixture was stirred and mixed to prepare an adhesive composition C1.
(例2～10)(Examples 2 to 10)
在例1的粘合剂组合物的制备中，以表1所示的方式设定单体成分和交联剂的种类和用量，对于其它内容与例1同样地进行，分别制备例2～10的粘合剂组合物C2～C10。In the preparation of the adhesive composition of Example 1, the types and amounts of monomer components and crosslinking agents were set as shown in Table 1, and the other contents were carried out in the same manner as in Example 1 to prepare adhesive compositions C2 to C10 of Examples 2 to 10, respectively.
(例11～14)(Examples 11-14)
在例1的粘合剂组合物的制备中，以表2所示的方式设定单体成分和交联剂的种类和用量，对于其它内容与例1同样地进行，分别制备例11～14的粘合剂组合物D1～D4。In the preparation of the adhesive composition of Example 1, the types and amounts of monomer components and crosslinking agents were set as shown in Table 2, and the other contents were carried out in the same manner as in Example 1 to prepare adhesive compositions D1 to D4 of Examples 11 to 14, respectively.
<半导体器件生产用耐热性压敏粘合片的制作><Preparation of heat-resistant pressure-sensitive adhesive sheet for semiconductor device production>
(实施例1)(Example 1)
在作为基材层的厚度为75μm的PET薄膜(商品名：双向拉伸聚酯薄膜，由南京亚博联新材料科技股份有限公司制造)的一侧涂布粘合剂组合物C1，然后干燥，形成厚度为25μm的第一粘合剂层。The adhesive composition C1 was coated on one side of a 75 μm thick PET film (trade name: biaxially oriented polyester film, manufactured by Nanjing Yabo Lian New Materials Technology Co., Ltd.) as a substrate layer, and then dried to form a first adhesive layer with a thickness of 25 μm.
然后，将55重量份聚二甲基硅氧烷“107硅橡胶”(深圳市吉鹏硅氟材料有限公司制造)、45重量份乙烯基MQ树脂“VSP8201-4”(成都博达爱福科技有限公司制造)、1.5重量份交联剂“91A”(江西蓝星星火有机硅有限公司制造)和2重量份铂催化剂“CATA 12070”(江西蓝星星火有机硅有限公司制造)添加到甲苯并均匀分散于甲苯中，将所得分散液施涂于基材层的另一侧，随后干燥，制备第二粘合剂层。由此，得到半导体器件生产用耐热性压敏粘合片。评价结果示于表3中。Then, 55 parts by weight of polydimethylsiloxane "107 silicone rubber" (manufactured by Shenzhen Jipeng Silicon Fluoride Material Co., Ltd.), 45 parts by weight of vinyl MQ resin "VSP8201-4" (manufactured by Chengdu Boda Aifu Technology Co., Ltd.), 1.5 parts by weight of crosslinking agent "91A" (manufactured by Jiangxi Bluestar Star Fire Silicone Co., Ltd.) and 2 parts by weight of platinum catalyst "CATA 12070" (manufactured by Jiangxi Bluestar Star Fire Silicone Co., Ltd.) are added to toluene and uniformly dispersed in toluene, and the resulting dispersion is applied to the other side of the substrate layer, followed by drying to prepare a second adhesive layer. Thus, a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production is obtained. The evaluation results are shown in Table 3.
第一粘合剂层在23℃下相对于不锈钢板(SUS430BA板)的180°剥离粘合力N1为0.11N/20mm。The first adhesive layer had a 180° peel adhesive force N1 of 0.11 N/20 mm at 23° C. with respect to a stainless steel plate (SUS430BA plate).
第一粘合剂层在130℃下加热5分钟后相对于不锈钢板(SUS430BA板)的180°剥离粘合力N2为0.13N/20mm。The first adhesive layer had a 180° peeling adhesive strength N2 of 0.13 N/20 mm with respect to a stainless steel plate (SUS430BA plate) after heating at 130° C. for 5 minutes.
第一粘合剂层在130℃下加热5分钟后相对于不锈钢板(SUS430BA板)的180°剥离粘合力N2与第一粘合剂层在23℃下相对于不锈钢板(SUS430BA板)的180°剥离粘合力N1之比，即N2/N1为1.18。The ratio of the 180° peel adhesion N2 of the first adhesive layer relative to the stainless steel plate (SUS430BA plate) after heating at 130°C for 5 minutes to the 180° peel adhesion N1 of the first adhesive layer relative to the stainless steel plate (SUS430BA plate) at 23°C, i.e. N2/N1, is 1.18.
(实施例2～10)(Examples 2 to 10)
除了使用表1中的粘合剂组合物C2～C10代替粘合剂组合物C1形成第一粘合剂层以外，以与实施例1相同的方式获得半导体器件生产用耐热性压敏粘合片。评价结果示于表3中。The evaluation results are shown in Table 3, except that the first adhesive layer was formed using Adhesive Compositions C2 to C10 in Table 1 instead of Adhesive Composition C1.
(比较例1～4)(Comparative Examples 1 to 4)
除了使用表2中的粘合剂组合物D1～D4代替粘合剂组合物C1形成第一粘合剂层以外，以与实施例1相同的方式获得半导体器件生产用耐热性压敏粘合片。评价结果示于表4中。The evaluation results are shown in Table 4, except that the first adhesive layer was formed using the adhesive compositions D1 to D4 in Table 2 instead of the adhesive composition C1.
<评价试验><Evaluation Test>
(1)180°剥离粘合力试验(1) 180° peel adhesion test
将各实施例及各比较例的压敏粘合片切取宽度20mm×长度150mm作为试验片。将用甲苯清洁化了的SUS板(SUS430BA板)作为被粘物，通过以下的步骤测定粘合力N1和粘合力N2。The pressure-sensitive adhesive sheets of each example and each comparative example were cut into test pieces of 20 mm width x 150 mm length. The adhesive strength N1 and the adhesive strength N2 were measured by the following procedure using a SUS plate (SUS430BA plate) cleaned with toluene as an adherend.
(粘合力N1的测定)(Measurement of Adhesion Strength N1)
在23℃、50％RH的标准环境下，将覆盖各试验片的粘合面的剥离衬垫剥落，使2kg的辊往返1次而将露出的粘合面压接于被粘物。将像这样操作而压接于被粘物的试验片在上述标准环境下放置30分钟后，根据JIS Z 0237，使用拉伸试验机(株式会社岛津制作所制造、产品名“Tensilon”)，以拉伸速度：300mm/分钟、剥离角度：180°进行剥离，测定该剥离所需要的力(180°剥离粘合力)(N/20mm)。测定结果示于表3和表4中。Under the standard environment of 23 ℃ and 50% RH, the release liner covering the adhesive surface of each test piece was peeled off, and the exposed adhesive surface was pressed to the adherend by a 2 kg roller back and forth once. After the test piece pressed to the adherend was placed under the above standard environment for 30 minutes, according to JIS Z 0237, a tensile tester (manufactured by Shimadzu Corporation, product name "Tensilon") was used to peel at a tension speed of 300 mm/min and a peeling angle of 180 ° to measure the force (180 ° peeling adhesive force) (N/20mm) required for the peeling. The measurement results are shown in Tables 3 and 4.
(粘合力N2的测定)(Measurement of Adhesion Strength N2)
将与粘合力N1的测定同样地操作而压接于被粘物的试验片在130℃下加热5分钟，接着在上述标准环境下放置30分钟后，同样地测定180°剥离粘合力。测定结果示于表3和表4中。The test piece pressure-bonded to the adherend in the same manner as in the measurement of the adhesive strength N1 was heated at 130°C for 5 minutes and then left in the above-mentioned standard environment for 30 minutes, and then the 180° peel adhesive strength was measured in the same manner. The measurement results are shown in Tables 3 and 4.
(2)15°剥离粘合力试验(2) 15° peel adhesion test
将实施例及比较例的压敏粘合片切取宽度20mm×长度150mm作为试验片。将用甲苯清洁化了的SUS板(SUS430BA板)作为被粘物，通过以下的步骤测定粘合力。The pressure-sensitive adhesive sheets of Examples and Comparative Examples were cut into test pieces of 20 mm in width and 150 mm in length. The adhesive strength was measured by the following procedure using a SUS plate (SUS430BA plate) cleaned with toluene as an adherend.
在23℃、50％RH的标准环境下，将覆盖各试验片的粘合面的剥离衬垫剥落，使2kg的辊往返1次而将露出的粘合面压接于被粘物。将像这样操作而压接于被粘物的试验片在上述标准环境下放置30分钟后，使用拉伸试验机(株式会社岛津制作所制造制造、商品名：“Tensilon”)，以拉伸速度：300mm/分钟、剥离角度：15°进行剥离，测定该剥离所需要的力(15°剥离粘合力)(N/20mm)。测定结果示于表3和表4中。Under the standard environment of 23°C and 50%RH, the release liner covering the adhesive surface of each test piece was peeled off, and a 2kg roller was reciprocated once to press the exposed adhesive surface onto the adherend. After the test piece pressed onto the adherend by such operation was placed under the above standard environment for 30 minutes, a tensile tester (manufactured by Shimadzu Corporation, trade name: "Tensilon") was used to peel at a tensile speed of 300 mm/min and a peeling angle of 15°, and the force (15° peeling adhesive force) (N/20 mm) required for the peeling was measured. The measurement results are shown in Tables 3 and 4.
将与上述23℃下的剥离粘合力的测定同样地操作而压接于被粘物的试验片在150℃下加热4小时，接着在上述标准环境下放置30分钟后，同样地测定15°剥离粘合力。测定结果示于表3和表4中。The test piece pressure-bonded to the adherend in the same manner as the above-mentioned measurement of the peel adhesive strength at 23°C was heated at 150°C for 4 hours, and then left in the above-mentioned standard environment for 30 minutes, and then the 15° peel adhesive strength was measured in the same manner. The measurement results are shown in Tables 3 and 4.
(3)储能模量测定(3) Storage modulus measurement
将粘合剂层冲裁成直径7.9mm，以用平行板夹持其的形式进行固定，将由此得到的样品作为测定试样。对于上述测定试样，使用动态粘弹性测定装置(Rheometric公司制造、产品名“ARES”)，在下述条件下进行动态粘弹性测定，测定23℃下的储能模量G'和150℃下的储能模量G'。粘合剂层的储能模量的测定结果示于表3和4。The adhesive layer was punched into a diameter of 7.9 mm and fixed by clamping it with parallel plates, and the sample obtained was used as a measurement sample. For the above-mentioned measurement sample, a dynamic viscoelasticity measurement device (manufactured by Rheometric Company, product name "ARES") was used to perform dynamic viscoelasticity measurement under the following conditions to measure the storage modulus G' at 23°C and the storage modulus G' at 150°C. The measurement results of the storage modulus of the adhesive layer are shown in Tables 3 and 4.
储能模量测定条件Storage modulus measurement conditions
测定模式：剪切模式Measurement mode: Shear mode
温度范围：-70℃～150℃Temperature range: -70℃～150℃
升温速度：5℃/分钟Heating rate: 5℃/min
测定频率：1HzMeasuring frequency: 1Hz
(4)包覆性(4) Coating
将半导体器件具有电极一侧的表面整齐地在贴合在上述实施例和比较例的压敏粘合片的第一粘合剂层上，置于真空压合机(TOWA株式会社制造)中，在模具的模腔内注入液体封装树脂，在1MPa压力、130℃下加热5分钟后，将粘合片去除，用显微镜(KEYENCECORPORATION制造，商品名：VHX-100，倍率：200倍)观察半导体器件电极面上是否有液体封装树脂渗入，并按照下述基准进行评价。The surface of the semiconductor device with the electrode side is neatly placed on the first adhesive layer of the pressure-sensitive adhesive sheet of the above-mentioned embodiment and comparative example, and placed in a vacuum laminating machine (manufactured by TOWA Corporation). Liquid encapsulation resin is injected into the mold cavity of the mold. After heating at a pressure of 1 MPa and 130°C for 5 minutes, the adhesive sheet is removed and a microscope (manufactured by KEYENCE CORPORATION, trade name: VHX-100, magnification: 200 times) is used to observe whether there is liquid encapsulation resin infiltration on the electrode surface of the semiconductor device, and evaluation is performed according to the following criteria.
○：液体封装树脂渗入半导体器件电极数量小于0.1％○: The amount of liquid encapsulation resin that penetrates into the semiconductor device electrodes is less than 0.1%
△：液体封装树脂渗入半导体器件电极数量为0.1％～1％△: The amount of liquid encapsulation resin that penetrates into the semiconductor device electrode is 0.1% to 1%
×：液体封装树脂渗入半导体器件电极数量大于1％×: The amount of liquid encapsulation resin that has penetrated into the semiconductor device electrodes is greater than 1%
(5)残胶性(5) Residual adhesive
将芯片具有电极一侧的表面贴合在上述实施例和比较例的压敏粘合片的第一粘合剂层上，放入烘箱中150℃加热4小时，然后将芯片从粘合片上剥离，用显微镜(KEYENCECORPORATION制造，商品名：VHX-100，倍率：200倍)观察上述芯片的粘贴面，目视确认芯片电极上有无残胶，按照下述基准进行评价。The surface of the chip with the electrode side is attached to the first adhesive layer of the pressure-sensitive adhesive sheet of the above-mentioned embodiment and comparative example, and heated in an oven at 150°C for 4 hours. The chip is then peeled off the adhesive sheet, and the bonding surface of the above-mentioned chip is observed under a microscope (manufactured by KEYENCE CORPORATION, trade name: VHX-100, magnification: 200 times) to visually confirm whether there is any residual glue on the chip electrode, and evaluation is performed according to the following criteria.
○：未确认到残胶○: No residual adhesive was found
×：确认到残胶×: Glue residue confirmed
(6)第一粘合剂层的固定性评价(6) Evaluation of fixation properties of the first adhesive layer
将上述实施例和比较例的压敏粘合片的第二粘合剂层贴合到SUS:304不锈钢基板上，将多个芯片具有电极一侧的表面整齐地贴合在压敏粘合片的第一粘合剂层上，在模具的模腔内用密封树脂一并密封后，用二次元量测仪(型号：“YVM-3020VT”，广东源兴恒准精密仪器有限公司制造)观察芯片在第一粘合剂层上的相对位置是否发生改变，若位置变动量超过0.005mm即认为是发生位置偏移，并按照下述基准进行评价。The second adhesive layer of the pressure-sensitive adhesive sheet of the above-mentioned embodiment and comparative example is bonded to a SUS:304 stainless steel substrate, and the surfaces of multiple chips having the electrode side are neatly bonded to the first adhesive layer of the pressure-sensitive adhesive sheet. After being sealed together with a sealing resin in the mold cavity of the mold, a two-dimensional measuring instrument (model: "YVM-3020VT", manufactured by Guangdong Yuanxing Hengzhun Precision Instrument Co., Ltd.) is used to observe whether the relative position of the chip on the first adhesive layer has changed. If the position change exceeds 0.005 mm, it is considered that a position shift has occurred, and it is evaluated according to the following criteria.
○：在第一粘合剂层上的芯片发生位置偏移的数量小于0.1％○: The number of chips on the first adhesive layer that were positionally shifted was less than 0.1%
△：在第一粘合剂层上的芯片发生位置偏移的数量为0.1％～1％△: The number of chips on the first adhesive layer that are shifted is 0.1% to 1%
×：在第一粘合剂层上的芯片发生位置偏移的数量大于1％×: The number of chips on the first adhesive layer that were positionally shifted was greater than 1%
(7)第二粘合剂层的固定性评价(7) Evaluation of fixation properties of the second adhesive layer
将上述实施例和比较例的压敏粘合片的第二粘合剂层贴合到SUS：304不锈钢基板上，将多个芯片具有电极一侧的表面整齐地贴合在压敏粘合片的第一粘合剂层上，在模具的模腔内用密封树脂一并密封后，在150℃下加热4小时后，将成型后的树脂切断成相应的大小，肉眼观察粘合片在不锈钢基板上是否发生位置滑移、边缘起翘或者脱落等粘合不良情况，并按照下述基准进行评价。The second adhesive layer of the pressure-sensitive adhesive sheet of the above-mentioned embodiment and comparative example was bonded to a SUS:304 stainless steel substrate, and the surfaces of a plurality of chips having electrodes were neatly bonded to the first adhesive layer of the pressure-sensitive adhesive sheet. After being sealed together with a sealing resin in the mold cavity, the molded resin was heated at 150°C for 4 hours, and then cut into corresponding sizes. The adhesive sheet was visually observed for poor adhesion such as position slippage, edge warping or falling off on the stainless steel substrate, and evaluated according to the following criteria.
○：无滑移、边缘起翘或者脱落等粘合不良情况发生○: No slippage, edge warping or falling off and other poor adhesion
×：有滑移、边缘起翘或者脱落等粘合不良情况发生×: Adhesion failure such as slippage, edge lifting or falling off occurs
(8)第一粘合剂层的剥离性评价(8) Evaluation of the releasability of the first adhesive layer
将多个芯片具有电极一侧的表面整齐地贴合在耐热性压敏粘合片的第一粘合剂层上，在150℃下加热4小时后，将PVC单面胶带(商品名：SPV-224，日东电工株式会社制造)贴在芯片另一侧，然后以180°剥离耐热性压敏粘合片，观察芯片是否从第一粘合剂层转移到PVC单面胶带上，并按照下述基准进行评价。The surfaces of multiple chips with electrodes on one side were neatly attached to the first adhesive layer of a heat-resistant pressure-sensitive adhesive sheet. After heating at 150°C for 4 hours, a PVC single-sided tape (trade name: SPV-224, manufactured by Nitto Denko Corporation) was attached to the other side of the chip. The heat-resistant pressure-sensitive adhesive sheet was then peeled off at 180° to observe whether the chip was transferred from the first adhesive layer to the PVC single-sided tape, and the evaluation was performed according to the following criteria.
○：残留在第一粘合剂层的芯片数量小于0.1％○: The number of chips remaining on the first adhesive layer is less than 0.1%
△：残留在第一粘合剂层的芯片数量为0.1～1％△: The number of chips remaining on the first adhesive layer is 0.1 to 1%
×：残留在第一粘合剂层的芯片数量大于1％×: The number of chips remaining in the first adhesive layer is greater than 1%
(9)第二粘合剂层的剥离性评价(9) Evaluation of the releasability of the second adhesive layer
将耐热性压敏粘合片的第二粘合剂层粘贴于SUS：304不锈钢基板上，在150℃下加热4小时，然后对耐热性压敏粘合片以15°进行剥离，通过主观手感确认能否容易地将剥离侧的第二粘合剂层从不锈钢基板上剥离，按照下述基准进行评价。The second adhesive layer of the heat-resistant pressure-sensitive adhesive sheet was attached to a SUS:304 stainless steel substrate and heated at 150°C for 4 hours. The heat-resistant pressure-sensitive adhesive sheet was then peeled off at 15°. Whether the second adhesive layer on the peeling side could be easily peeled off from the stainless steel substrate was confirmed by subjective feel and evaluated according to the following criteria.
○：非常容易剥离○: Very easy to peel off
△：较容易剥离△: Easier to peel off
×：不易剥离×: Not easy to peel off
(10)综合评价(10) Comprehensive evaluation
根据上述各评价结果，按照下述标准进行综合评价。Based on the above evaluation results, a comprehensive evaluation was performed according to the following criteria.
○：综合效果优异○: Excellent overall effect
△：综合效果良好△: Good overall effect
×：综合效果差×: Poor overall effect
表1Table 1
表2Table 2
表3Table 3
表4Table 4
由表3可知，本发明的半导体器件生产用耐热性压敏粘合片能够支持芯片以便芯片在树脂包封步骤期间不转移，减少芯片从指定位置的偏移。另外，本发明的半导体器件生产用耐热性压敏粘合片能够在使用之后轻轻剥离，包封后对于包封树脂及芯片不发生残胶污染。As can be seen from Table 3, the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention can support the chip so that the chip does not shift during the resin encapsulation step, reducing the chip from the specified position. In addition, the heat-resistant pressure-sensitive adhesive sheet for semiconductor device production of the present invention can be gently peeled off after use, and no residual adhesive contamination occurs to the encapsulation resin and the chip after encapsulation.
然而，在比较例1～4中，如表4所示，芯片从指定位置偏移，并且使用之后不易剥离，产生剥离后的残胶污染。However, in Comparative Examples 1 to 4, as shown in Table 4, the chips were shifted from the designated positions and were difficult to peel off after use, resulting in residual adhesive contamination after peeling.
产业上的可利用性Industrial Applicability
本发明能够提供半导体器件生产用耐热性压敏粘合片，当生产无基板半导体封装体时其用于临时固定芯片，所述粘合片在树脂包封步骤中支持芯片并且由于随后的热处理通过压敏粘合剂层的固化而能够减少残胶。并且所述粘合片可在树脂包封步骤期间确定地支持芯片，芯片从指定位置的偏移小。The present invention can provide a heat-resistant pressure-sensitive adhesive sheet for semiconductor device production, which is used for temporarily fixing a chip when producing a substrate-less semiconductor package, the adhesive sheet supports the chip in a resin encapsulation step and can reduce adhesive residue due to subsequent heat treatment by curing of a pressure-sensitive adhesive layer. And the adhesive sheet can surely support the chip during the resin encapsulation step, and the chip is less deviated from a specified position.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910621802.7ACN112210313B (en) | 2019-07-10 | 2019-07-10 | Heat-resistant pressure-sensitive adhesive sheet for semiconductor device production |
| KR1020200064700AKR20210007828A (en) | 2019-07-10 | 2020-05-29 | Heat resistant pressure sensitive adhesive sheet for semiconductor device production |
| TW109121142ATWI868165B (en) | 2019-07-10 | 2020-06-22 | Heat-resistant pressure-sensitive adhesive sheets for semiconductor device production |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910621802.7ACN112210313B (en) | 2019-07-10 | 2019-07-10 | Heat-resistant pressure-sensitive adhesive sheet for semiconductor device production |
| Publication Number | Publication Date |
|---|---|
| CN112210313A CN112210313A (en) | 2021-01-12 |
| CN112210313Btrue CN112210313B (en) | 2023-10-27 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910621802.7AActiveCN112210313B (en) | 2019-07-10 | 2019-07-10 | Heat-resistant pressure-sensitive adhesive sheet for semiconductor device production |
| Country | Link |
|---|---|
| KR (1) | KR20210007828A (en) |
| CN (1) | CN112210313B (en) |
| TW (1) | TWI868165B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230144306A (en)* | 2022-04-07 | 2023-10-16 | 주식회사 엘지화학 | Adhesive film for semiconductor and semiconductor package using the same |
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| JP2009079203A (en)* | 2007-09-06 | 2009-04-16 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive product and display using it |
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| CN102134453A (en)* | 2009-12-22 | 2011-07-27 | 日东电工株式会社 | Heat resistant adhesive sheet used in the fabrication of substrateless semiconductor package |
| JP2012214543A (en)* | 2011-03-31 | 2012-11-08 | Lintec Corp | Pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
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| JP2009079203A (en)* | 2007-09-06 | 2009-04-16 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive product and display using it |
| JP2011105830A (en)* | 2009-11-16 | 2011-06-02 | Lintec Corp | Pressure sensitive adhesive composition, pressure sensitive adhesive and optical film |
| CN102134453A (en)* | 2009-12-22 | 2011-07-27 | 日东电工株式会社 | Heat resistant adhesive sheet used in the fabrication of substrateless semiconductor package |
| JP2012214543A (en)* | 2011-03-31 | 2012-11-08 | Lintec Corp | Pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
| CN103131339A (en)* | 2011-11-25 | 2013-06-05 | 日东电工株式会社 | Adhesive tape |
| JP2013199630A (en)* | 2012-02-23 | 2013-10-03 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet |
| CN103360974A (en)* | 2012-03-30 | 2013-10-23 | 日东电工株式会社 | Adhesive sheet |
| CN104031570A (en)* | 2013-03-04 | 2014-09-10 | 日东电工株式会社 | Heat-peelable adhesive sheet |
| CN105907317A (en)* | 2015-02-24 | 2016-08-31 | 日东电工株式会社 | Heat-peelable pressure-sensitive adhesive sheet |
| WO2017056927A1 (en)* | 2015-09-29 | 2017-04-06 | 日東電工株式会社 | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, optical film with pressure-sensitive adhesive layer, and image display device |
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| CN112210313A (en) | 2021-01-12 |
| TWI868165B (en) | 2025-01-01 |
| KR20210007828A (en) | 2021-01-20 |
| TW202102627A (en) | 2021-01-16 |
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